Phthalocyanine dye and use thereof for ink-jet printing

ABSTRACT

The present invention relates to a phthalocyanine colorant characterized in that it has, as substituents, at least one unsubstituted sulfamoyl group and at least one substituted sulfamoyl group, the total number of these groups being 2 to 4, the substituent on the substituted sulfamoyl group has a substituted triazinyl group bonded thereto through a crosslinking group, and the unsubstituted sulfamoyl group and the substituted sulfamoyl group are bonded to the phthalocyanine ring at the β-position. Said phthalocyanine colorant is suitable for use in an ink, especially a cyan ink, for an ink-jet printer. A printed matter obtained by printing with said ink is excellent in light fastness, ozone fastness and moisture fastness.

TECHNICAL FIELD

The present invention relates to a phthalocyanine colorant, an ink, anink set, an ink-jet recording method using the ink or the ink set, acolored product and a method for producing the phthalocyanine colorant.

BACKGROUND OF THE INVENTION

Lately in the field of an image recording material, particularly, amaterial for forming a color image has been prevalently used, includingspecifically such as an ink-jet recording material, an image recordingmaterial of heat-sensitive transcription type, a recording materialusing an electronic photography method, a silver halide photosensitivematerial of transcription type, a printing ink and a recording pen. ForLCD and PDP in a display field and for electronic parts of CCD in thefield of a movie camera, a color filter is used. In these color imagerecording materials and color filters, to reproduce or record afull-colored image, a colorant (dye and pigment) of so-called threeprimary colors in an additive color-mixing method or a subtractivecolor-mixing method is used. At present, however, a colorant havingabsorption characteristics to realize a desirable color-reproducingrange and fastness to various conditions of use is not actuallyavailable and improvement is strongly required.

An ink-jet recording method has rapidly become prevalent and beendeveloping further because of an inexpensive material, high-speedrecording capability, low noise in recording and easy color recording. Amethod for ink-jet recording includes a continuous method to sprayliquid droplets continuously and an on-demand method to spray liquiddroplets according to an image information signal. A method for jettingthe liquid droplets includes such as a method for jetting liquiddroplets by pressurization using piezoelectric elements, a method forjetting liquid droplets by generation of bubbles in an ink by heating, amethod for using an ultrasonic wave and a method for sucking and jettingliquid droplets by static electricity force. An ink suitable for ink-jetrecording includes, for example, a water-based ink, an oil-based ink anda solid (melt type) ink.

A colorant to be used for the ink suitable for such ink-jet recording isrequired to have high solubility or dispersibility in a solvent, to becapable of high-concentration recording, to have good hue, to havesatisfactory fastness against light, heat and an active gas (forexample, an oxidizing gas such as NO_(x) and ozone, and SO_(x)) in theenvironment, to have superior fastness against water and chemicals, tohave good fixation on a recording material with little blurring, to besuperior in shelf life as an ink, to be free from toxicity and furtherto be available at a low price. In particular, such a cyan colorant hasbeen strongly desired as has good cyan hue, along with excellent lightfastness (durability to light), ozone fastness (durability to ozone gas)and moisture fastness (durability under high humidity) and free frombronze phenomenon (also called bronzing phenomenon). Bronze phenomenonmeans phenomenon that a colorant glares like metal chips on the surfaceof a glossy paper, and the like caused by colorant association orinsufficient absorption of an ink. This phenomenon impairs gloss, printquality and print concentration.

Typical skeleton of a water-soluble cyan colorant to be used for an inksuitable for ink-jet recording include phthalocyanines andtriphenylmethanes. A typical phthalocyanine series colorant reported andused most widely includes the following phthalocyanine derivativesclassified into A to H.

A: A known phthalocyanine series colorant such as Direct Blue 86, DirectBlue 87, Direct Blue 199, Acid Blue 249 and Reactive Blue 71.

B: A phthalocyanine series colorant disclosed in JP Laid-Open No.190273/1987 (Literature 1), JP Laid-Open No. 138511/1995 (Literature 2),JP Laid-Open No. 105349/2002 (Literature 3) and the like [for example,Cu—Pc—(SO₃Na)_(m)(SO₂NH₂)_(n): a mixture wherein m+n=1 to 4].

C: A phthalocyanine series colorant disclosed in JP Laid-Open No.171085/1993 (Literature 4) and the like [for example,Cu—Pc—(CO₂H)_(m)(CONR₁R₂)_(n): m+n=0 to 4].

D: A phthalocyanine series colorant disclosed in JP Laid-Open No.140063/1998 (Literature 5) and the like [for example,Cu—Pc—(SO₃H)_(m)(SO₂NR₁R₂)_(n): m+n=1 to 4; and m≠0].

E: A phthalocyanine series colorant disclosed in JP Laid-Open No.515048/1999 (Literature 6) and the like [for example,Cu—Pc—(SO₃H)l(SO₂NH₂)_(m)(SO₂NR₁R₂)_(n): l+m+n=0 to 4].

F: A phthalocyanine series colorant disclosed in JP Laid-Open No.22967/1984 (Literature 7) and the like [for example,Cu—Pc—(SO₂NR₁R₂)_(n): n=1 to 5].

G: A phthalocyanine series colorant disclosed in JP Laid-Open No.303009/2000 (Literature 8), JP-A-2002-249677/2002 (Literature 9) and thelike [a phthalocyanine compound with substituents at controlledpositions, a phthalocyanine series colorant with substituents at theβ-position: On the β-position, see description at the later section].

H: A phthalocyanine series colorant having a pyridine ring disclosed inJP Laid-Open No. 34758/2003 (Literature 10) and the like.

A phthalocyanine series colorant used prevalently today and representedby Direct Blue 86 or Direct Blue 199 is characterized by having superiorlight fastness to a generally known magenta dye or yellow dye. Aphthalocyanine series colorant gives a greenish hue under acidicconditions, and thus is not very preferable as a cyan ink. Therefore,when these dyes are used as a cyan ink, it is preferable to use themunder neutral to basic conditions. However, even when an ink is used inneutral to basic conditions, a printed hue possibly undergoes a bigchange on an acid recording paper.

Moreover, an oxidizing gas such as a nitrogen oxide gas and ozone thatis often writing up lately as an environmental issue causes the color tochange to a greenish hue and to fade, and optical density of printing todeteriorate.

On the other hand, a triphenylmethane series dye is much inferior inlight fastness, ozone fastness and moisture fastness although its hue isgood.

With increase in application field being used in a display such as anadvertisement in the future, leading to more chances of getting exposedto light and active gases in the environment, such an inexpensivecolorant and ink will be more and more required as has good hue andsuperior fastness against light and an active gas (for example, anoxidizing gas such as NO_(x) and ozone, and SO_(x)) in the environment.However, it is difficult to develop such a cyan colorant (for example,phthalocyanine series colorant) and a cyan ink as satisfies theserequirements at a high level. Although a phthalocyanine series colorantswith active-gas fastness have been disclosed so far in the aboveLiteratures 3 and 8 to 10 and JP Laid-Open No. 80762/2002 (Literature11), such a cyan colorant and a cyan ink have not yet been obtained ascan satisfy all qualities such as hue, light fastness, ozone fastnessand moisture fastness and be produced at a low cost. Accordingly, marketrequirements have not yet been satisfied sufficiently.

A subject of the present invention is to solve the above conventionalproblems and attain the following object. Specifically, an object of thepresent invention is to provide a novel phthalocyanine colorant that hasgood hue as a cyan ink and is superior in light fastness, ozone fastnessand moisture fastness, an ink suitable for an ink-jet using saidphthalocyanine colorant and an ink-jet recording method.

DISCLOSURE OF THE INVENTION

After studying in detail phthalocyanine series colorants having goodhue, excellent light fastness and ozone fastness, the present inventorshave found that the above problems can be solved by using a specificphthalocyanine series colorant as a colorant for an ink and thus havecompleted the present invention. In more detail, the present inventionrelates to a metallo phthalocyanine colorant represented by Formula (1)as shown below, having both a sulfamoyl group substituted bysubstituents having triazinyl ring and an unsubstituted sulfamoyl groupat a specific substitution position (β-position: to be described later),the present inventors have found that said has good cyan hue and issuperior in light fastness (durability to light), moisture fastness(durability under high humidity) and also ozone fastness (durability toozone gas) and free from bronze phenomenon (also called bronzingphenomenon) and have completed the present invention. The presentinvention will be described in detail hereinbelow.

1. A phthalocyanine colorant represented by Formula (1):

[in Formula (1), M represents a hydrogen atom, a metal atom, a metaloxide, a metal hydroxide, or a metal halide; R₂, R₃, R₆, R₇, R₁₀, R₁₁,R₁₄ and R₁₅ each independently represent an unsubstituted sulfamoylgroup represented by Formula (2), a substituted sulfamoyl grouprepresented by Formula (3), or a hydrogen atom, provided that at leastone of R₂, R₃, R₆, R₇, R₁₀, R₁₁, R₁₄ and R₁₅ is an unsubstitutedsulfamoyl group, and at least one thereof is a substituted sulfamoylgroup represented by Formula (3); and R₁, R₄, R₅, R₈, R₉, R₁₂, R₁₃ andR₁₆ represent hydrogen atoms; the sum of a number of an unsubstitutedsulfamoyl group and a number of a substituted sulfamoyl group is 2 to 4,and a number of an unsubstituted sulfamoyl group is 1 to 3 and a numberof a substituted sulfamoyl group is

[in Formula (3), R₁₇ and R₁₈ each independently represent a hydrogenatom, a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted heterocyclic group, and asubstituted or unsubstituted alkenyl group; A represents a crosslinkinggroup, and adjacent R₁₇, R₁₈ and A may form a ring by bonding together;Y and Z each independently represent a halogen atom, a hydroxyl group, asulfonic acid group, a carboxyl group, an amino group, a substituted orunsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxygroup, a substituted or unsubstituted aryloxyl group, a substituted orunsubstituted heterocyclic oxy group, a substituted or unsubstitutedalkenyloxy group, a substituted or unsubstituted alkylamino group, asubstituted or unsubstituted cycloalkylamino group, a substituted orunsubstituted arylamino group, a substituted or unsubstitutedheterocyclic amino group, a substituted or unsubstituted alkenylaminogroup, a substituted or unsubstituted dialkylamino group, a substitutedor unsubstituted alkylthio group, a substituted or unsubstitutedarylthio group, a substituted or unsubstituted heterocyclic thio group,a substituted or unsubstituted alkenylthio group, provided that at leastone of Y and Z is a group having an ionic and hydrophilic group as asubstituent.]

2. The phthalocyanine colorant according to claim 1, wherein Formula (1)according to claim 1 is represented by Formula (4) wherein M is Cu:

[wherein R₁ to R₁₆ mean the same as in Formula (1)].

3. The phthalocyanine colorant according to claim 1 or 2, wherein thecrosslinking group A is an alkylene, a cycloalkylene, or an arylenegroup.

4. The phthalocyanine colorant according to any one of claims 1 to 3,wherein in each of combinations of R₂ and R₃, R₆ and R₇, R₁₀ and R₁₁,and R₁₄ and R₁₅, one member of each combination is a hydrogen atom, andthe other is an unsubstituted sulfamoyl group represented by Formula(2), a substituted sulfamoyl group represented by Formula (3) or ahydrogen atom, and among R₂, R₃, R₆, R₇, R₁₀, R₁₁, R₁₄ and R₁₅, at leastone is an unsubstituted sulfamoyl group and at least one is asubstituted sulfamoyl group represented by Formula (3).

5. The phthalocyanine colorant according to claim 1 or 2, wherein asubstituted sulfamoyl group of Formula (3) is a group represented byFormula (5) as shown below:

[in Formula (5), B represents an alkylene, arylene, or xylylene group; Dand E each independently represent a chlorine atom, a hydroxyl group, asulfonic acid group, a carboxyl group, an amino group, an alkoxy group(which may be substituted with a substituent selected from a groupconsisting of a sulfonic acid group, a carboxyl group, a hydroxyl group,a dialkylamino group, an arylamino group, an acetylamino group, analkoxy group, an aryl group, a cyano group and a halogen atom), aphenoxyl group (which may be substituted with one or two or moresubstituents selected from a group consisting of a sulfonic acid group,a carboxyl group, a ureide group, an alkyl group and an alkoxy group), anaphthoxyl group (which may be substituted with one or two or moresubstituents selected from a group consisting of a sulfonic acid groupand an acetylamino group), a benzyloxyl group (which may be substitutedwith a sulfonic acid group), a phenetyloxyl group (which may besubstituted with a sulfonic acid group), an alkylamino group (which maybe substituted with a substituent selected from a group consisting of asulfonic acid group, a carboxyl group, a hydroxyl group, an alkoxygroup, a dialkylamino group, an arylamino group, an aryl group, ahalogen atom and a cyano group), an anilino group (which may besubstituted with one or two or more substituents selected from a groupconsisting of a sulfonic acid group, a carboxyl group, a hydroxyl group,a dialkylamino group, an arylamino group, an acetylamino group, a ureidegroup, an alkyl group, an alkoxy group, a nitro group, a cyano group, aheterocyclic group and a halogen atom), a naphtylamino group (which maybe substituted with a sulfonic acid group or a hydroxyl group), abenzylamino group (which may be substituted with a sulfonic acid group),a phenetylamino group (which may be substituted with a sulfonic acidgroup), an alkylthio group (which may be substituted with a sulfonicacid group, a carboxylic group or a hydroxyl group), or an arylthiogroup (which may be substituted with one or two or more substituentsselected from a group consisting of a sulfonic acid group, a carboxylgroup, a hydroxyl group, and an alkyl group), and at least one of D andE has, as a substituent, an ionic and hydrophilic group selected from agroup consisting of a sulfonic acid group and a carboxyl group.]

6. The phthalocyanine colorant according to claim 1, wherein either oneof Y and Z is an amino group, or a substituted or unsubstitutedalkylamino group, and the other is a group other than a halogen and ahydroxyl group.

7. The phthalocyanine colorant according to claim 6, wherein a groupother than a halogen and a hydroxyl group is an arylamino groupsubstituted with a sulfonic acid group.

8. The phthalocyanine colorant according to claim 1, wherein content ofa colorant of Formula (1) is at least 60% based on the total amount ofcolorants.

9. The phthalocyanine colorant according to any one of claims 1 to 8,wherein the colorant of Formula (1) is obtained by subjecting thephthalocyanine colorant or the salt thereof represented by Formula (6)to a reaction with a chlorinating reagent to convert a sulfonic acidgroup to a chlorosulfonic acid group, followed by further reaction withan organic amine represented by Formula (X) as shown below and anamidating reagent:

[in Formula (6), M represents a hydrogen atom, a metal atom, a metaloxide, a metal hydroxide or a metal halide; L represents a hydrogenatom, an alkali metal ion, an alkali earth metal ion, an onium ion of anorganic amine or an ammonium ion; a, b, c and d is 0 or 1, and the sumthereof is an integer of 2 to 4.]:

[in Formula (X), R₁₇ and R₁₈ each independently represent a hydrogenatom, a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted heterocyclic group, and asubstituted or unsubstituted alkenyl group; A represents a crosslinkinggroup, and adjacent R₁₇, R₁₈ and A may form a ring by bonding together;Y and Z each independently represent a halogen atom, a hydroxyl group, asulfonic acid group, a carboxyl group, an amino group, a substituted orunsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxygroup, a substituted or unsubstituted aryloxyl group, a substituted orunsubstituted heterocyclic oxy group, a substituted or unsubstitutedalkenyloxy group, a substituted or unsubstituted alkylamino group, asubstituted or unsubstituted cycloalkylamino group, a substituted orunsubstituted arylamino group, a substituted or unsubstitutedheterocyclic amino group, a substituted or unsubstituted alkenylaminogroup, a substituted or unsubstituted dialkylamino group, a substitutedor unsubstituted alkylthio group, a substituted or unsubstitutedarylthio group, a substituted or unsubstituted heterocyclic thio group,a substituted or unsubstituted alkenylthio group, provided that at leastone of Y and Z is a group having an ionic and hydrophilic group as asubstituent.]

10. A phthalocyanine colorant, which is obtained by subjectingderivatives of 4-sulfophthalic acid to reaction with themselves orsubjecting a derivative of 4-sulfophthalic acid to reaction with aderivative of a phthalic acid (anhydride) in the presence of a metalliccompound to obtain a sulfometallo phthalocyanine compound, which isreacted with a chlorinating reagent to convert a sulfonic acid group toa chlorosulfonic acid group, followed by further reaction with anamidating reagent and an organic amine represented by Formula (X) asshown below:

(in Formula (X), R₁₇, R₁₈, A, Y and Z represent the same meaning asdescribed above.]

11. The phthalocyanine colorant according to claim 10, wherein thecrosslinking group A is an alkylene, a cycloalkylene, or an arylenegroup.

12. The phthalocyanine colorant according to claim 10 or 11, wherein theorganic amine represented by Formula (X) is represented by Formula (X′)as shown below:

[in Formula (X′), B represents an alkylene, an arylene, or a xylylenegroup; D and E each independently represent a chlorine atom, a hydroxylgroup, a sulfonic acid group, a carboxyl group, an amino group, analkoxy group (which may be substituted with a substituent selected froma group consisting of a sulfonic acid group, a carboxyl group, ahydroxyl group, a dialkylamino group, an arylamino group, an acetylaminogroup, an alkoxy group, an aryl group, a cyano group and a halogenatom), a phenoxyl group (which may be substituted with one or two ormore substituents selected from a group consisting of a sulfonic acidgroup, a carboxyl group, a ureide group, an alkyl group and an alkoxygroup), a naphthoxyl group (which may be substituted with one or two ormore substituents selected from a group consisting of a sulfonic acidgroup and an acetylamino group), a benzyloxyl group (which may besubstituted with a sulfonic acid group), a phenetyloxyl group (which maybe substituted with a sulfonic acid group), an alkylamino group (whichmay be substituted with a substituent selected from a group consistingof a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkoxygroup, a dialkylamino group, an arylamino group, an aryl group, ahalogen atom and a cyano group), an anilino group (which may besubstituted with one or two or more substituents selected from a groupconsisting of a sulfonic acid group, a carboxyl group, a hydroxyl group,a dialkylamino group, an arylamino group, an acetylamino group, a ureidegroup, an alkyl group, an alkoxy group, a nitro group, a cyano group, aheterocyclic group and a halogen atom), a naphtylamino group (which maybe substituted with a sulfonic acid group or a hydroxyl group), abenzylamino group (which may be substituted with a sulfonic acid group),a phenetylamino group (which may be substituted with a sulfonic acidgroup), an alkylthio group (which may be substituted with a sulfonicacid group, a carboxylic group or a hydroxyl group), or an arylthiogroup (which may be substituted with one or two or more substituentsselected from a group consisting of a sulfonic acid group, a carboxylgroup, a hydroxyl group and an alkyl group); and at least one of D and Ehas, as a substituent, an ionic and hydrophilic group selected from agroup consisting of a sulfonic acid group and a carboxyl group.]

13. The phthalocyanine colorant according to any one of claims 10 to 12,wherein the metallic compound is a copper compound.

14. An ink characterized by comprising, as a colorant component, thephthalocyanine colorant according to any one of claims 1 to 13.

15. The ink according to claim 14, which comprises an organic solvent.

16. The ink according to claims 14 or 15, which is for ink-jet recordinguse.

17. An ink set characterized by using the ink according to any one ofclaims 14 to 16 as at least one kind in an ink-jet printer which uses atleast two kinds of cyan inks having different colorant concentrations.

18. An ink-jet recording method characterized by using, as an ink, theink or the ink set according to any one of claims 14 to 17, in anink-jet recording method wherein recording is conducted onto a recordingmaterial by jetting ink droplets in response to recording signals.

19. The ink-jet recording method according to claim 18, wherein therecording material is a sheet for information transmission.

20. The ink-jet recording method according to claim 19, wherein thesheet for information transmission is a surface-treated sheet and asheet having an ink image receiving layer which contains white inorganicpigment particles on a backing material.

21. A container comprising the ink or the ink set according to any oneof claims 14 to 17.

22. An ink-jet printer comprising the container according to claim 21.

23. A colored product which is colored with the ink or the ink setaccording to any one of claims 14 to 17.

24. A method for producing a phthalocyanine colorant characterized bybeing obtained by subjecting derivatives of 4-sulfophthalic acid toreaction with themselves or subjecting a derivative of 4-sulfophthalicacid to reaction with a derivative of a phthalic acid (anhydride) in thepresence of a copper compound to obtain a compound or a salt thereof,which is reacted with a chlorinating reagent to convert a sulfonic acidgroup to a chlorosulfonyl group, followed by further reaction with anorganic amine represented by the above Formula (X) and an amidatingreagent.

25. A phthalocyanine colorant which has not less than 60% of a compoundsubstituted at the β-position and not more than 40% of a compoundsubstituted at the α-position in a phthalocyanine colorant representedby Formula (14) as shown below:

[wherein M represents a hydrogen atom, a metal atom, a metal oxide, ametal hydroxide or a metal halide; 1 includes 0 and lower than 1; n isnot smaller than 0.3 and not larger than 3; m is not smaller than 1 andnot larger than 3.7, and the sum of l, m and n is not smaller than 2 andnot larger than 4; R₁₇ and R₁₈ each independently represent a hydrogenatom, a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted heterocyclic group, and asubstituted or unsubstituted alkenyl group; and A represents acrosslinking group, and adjacent R₁₇, R₁₈ and A may form a ring bybonding together; Y and Z each independently represent a halogen atom, ahydroxyl group, a sulfonic acid group, a carboxyl group, an amino group,a substituted or unsubstituted alkoxy group, a substituted orunsubstituted cycloalkyloxy group, a substituted or unsubstitutedaryloxyl group, a substituted or unsubstituted heterocyclic oxy group, asubstituted or unsubstituted alkenyloxy group, a substituted orunsubstituted alkylamino group, a substituted or unsubstitutedcycloalkylamino group, a substituted or unsubstituted arylamino group, asubstituted or unsubstituted heterocyclic amino group, a substituted orunsubstituted alkenylamino group, a substituted or unsubstituteddialkylamino group, a substituted or unsubstituted alkylthio group, asubstituted or unsubstituted arylthio group, a substituted orunsubstituted heterocyclic thio group, a substituted or unsubstitutedalkenylthio group, provided that at least one of Y and Z is a grouphaving an ionic and hydrophilic group as a substituent.]

26. The phthalocyanine colorant according to claim 25, wherein eitherone of Y and Z is an amino group, or a substituted or unsubstitutedalkylamino group, and the other is a group other than a halogen and ahydroxyl group.

27. The phthalocyanine colorant according to claim 26, wherein a groupother than a halogen and a hydroxyl group is an arylamino groupsubstituted with a sulfonic acid group.

28. The phthalocyanine colorant according to claim 25, wherein Mrepresents a copper atom; A represents a divalent crosslinking grouphaving carbon atoms of 1 to 6; 1 includes 0 and smaller than 1; n is notsmaller than 0.3 and not larger than 3; m is not smaller than 1 and nothigher than 3.7; and the sum of l, m and n is 2 to 4; both R₁₇ and R₁₈represent hydrogen atoms; Y and Z each independently represent an aminogroup, a substituted or unsubstituted alkylamino group, a substituted orunsubstituted arylamino group, a substituted or unsubstituteddialkylamino group, provided that at least one of Y and Z is a grouphaving an ionic and hydrophilic group as a substituent.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail hereinbelow.

A colorant of the present invention represented by the above Formula (1)is obtained by subjecting 4-sulfophthalic acid derivatives to reactionwith themselves or subjecting a 4-sulfophthalic acid derivative toreaction with a phthalic acid (phthalic anhydride) derivative in thepresence of a metallic compound, followed by reaction of thus obtainedproduct with a chlorination agent to convert a sulfonic acid group to achlorosulfonyl group, further reaction with an amidation agent and aspecific organic amine and introducing an unsubstituted sulfamoyl groupand a substituted sulfamoyl group at a specific substitution position(β-position) of a phthalocyanine ring. A printed material using saidcolorant shows very superior fastness to ozone gas.

In general, a phthalocyanine derivative may contain substitutionposition isomers of substituents R₁ to R₁₆ in Formula (1) as shownbelow, that are formed inevitably in synthesizing thereof and thesesubstitution position isomers are often regarded as the same derivativeswithout being distinguished each other:

Formula (1)

(In Formula (1), M and R₁ to R₁₆ represent each the same meaning as theabove).

For the sake of convenience in the present description, three kinds ofphthalocyanine derivatives having a different substitution position areclassified as defined below into a substitution type at the β-position(1), an substitution type at the α-position (2) and a mixed substitutiontype at α- and β-positions (3), which are used in explainingphthalocyanine derivatives having different substitution positions.

In the following explanation, the 1st to the 16th substitution positionsrepresent the position on a benzene ring to which substituent of R₁ toR₁₆ is bonded, respectively, which should be similar hereinbelow in thepresent description.

(1) a substitution type at the β-position: a phthalocyanine coloranthaving a specific substituent (a sulfonic acid group, a sulfamoyl groupor a substituted sulfamoyl group in the present description) at the 2ndand/or 3rd, 6th and/or 7th, 10th and/or 11th, and 14th and/or 15thpositions.

(2) a substitution type at the α-position: a phthalocyanine coloranthaving a specific substituent at the 1st and/or 4th, 5th and/or 8th, 9thand/or 12th, and 13th and/or 16th positions.

(3) a mixed substitution type at the α- and β-positions: aphthalocyanine colorant having a specific substituent at an optionalposition among the 1st to 16th positions.

A phthalocyanine colorant of the present invention represented byFormula (1) belongs to the above substitution type at the β-position.Whether a substituted phthalocyanine colorant produced using a methodfor the present invention is a substitution type at the β-position or asubstitution type at the α-position or a mixed substitution type at theα- and β-positions can be predicted from position of a substituent in araw material, a phthalic acid derivative (because thus obtainedphthalocyanine colorant has also a substituent at the correspondingposition). Otherwise, the type of a phthalocyanine colorant can beconfirmed by decomposing it to a phthalic acid derivative using nitricacid, and the like, and examining the substitution position in thederivative using NMR.

In the above Formula (1), M represents a hydrogen atom, a metal atom, ametal oxide, a metal hydroxide or a metal halide. A metal atom includesspecifically, for example, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W,Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, g, Au, Zn, Cd, Hg, Al, Ga,In, Si, Ge, Sn, Pb, Sb, and Bi. A metal oxide includes such as VO andGeO. A metal hydroxide includes, for example, Si(OH)₂, Cr(OH)₂, Sn(OH)₂and AlOH. A metal halide includes, for example, SiCl₂, VCl, VCl₂, VOCl,FeCl, GaCl, ZrCl and AlCl. Among these, Cu, Ni, Zn, Al and AlOH arepreferable and Cu is most preferable.

Unless otherwise stated in the present description, the number of carbonatoms is not limited especially in an alkyl group, an alkoxy group, analkenyl group, a cycloalkyl group, an alkylene group and the like, aslong as the object of the present invention can be attained. Theapproximate number of carbon atoms in these groups is usually 1 to 16,preferably 1 to 12, more preferably 1 to 6 and still more preferably 1to 4. However, it is usually 3 to 12, preferably about 5 to 8 in acycloalkyl group. The kind of a substituent contained in these groups isnot limited especially as long as the object of the present inventioncan be attained. A preferable substituent on the carbon chain of thesegroups includes, for example, a sulfonic acid group and a group derivedtherefrom (sulfamoyl group, etc.), a carboxyl group and a group derivedtherefrom (carboxylate ester group, etc.), a phosphoric acid group and agroup derived therefrom (phosphate ester group, etc.), a hydroxyl group,a substituted or unsubstituted alkoxy group, a substituted orunsubstituted amino group, a substituted or unsubstituted aryl group, ahalogen atom and a cyano group.

The kind of an aryl group is not limited especially as long as theobject of the present invention can be attained. A phenyl group or anaphthyl group is usually used. A preferable substituent on an arylgroup includes, for example, a substituent mentioned as a preferablesubstituent on the above carbon chain, and a ureido group, a nitro groupand a heterocyclic group.

In the above Formula (3) and Formula (X), R₁₇ and R₁₈ represent eachindependently a hydrogen atom, a substituted or unsubstituted alkylgroup, a substituted or unsubstituted cycloalkyl group, a substituted orunsubstituted aryl group, a substituted or unsubstituted heterocyclicgroup and a substituted or unsubstituted alkenyl group.

The above substituted or unsubstituted alkyl group includes, forexample, an alkyl group of 1 to 12 carbon atoms. Said substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an alkoxy group, an amino group(which may be substituted with an alkyl group, an aryl group and anacetyl group), an aryl group, a halogen atom and a cyano group.

The above substituted or unsubstituted cycloalkyl group includes, forexample, a cycloalkyl group of 3 to 12 carbon atoms, preferably acycloalkyl group of 5 to 8 carbon atoms. Said substituent in thecycloalkyl group includes, for example, a sulfonic acid group, acarboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxygroup, an amino group (which may be substituted with an alkyl group, anaryl group and an acetyl group), an aryl group, a halogen atom and acyano group.

An alkyl group of the above alkyl group substituted with the above arylgroup (an aralkyl group) has preferably about 1 to 12 carbon atoms. Saidaralkyl group may have a substituent that includes, for example, asulfonic acid group, a carboxyl group, a phosphoric acid group, ahydroxyl group, an alkoxy group, an amino group (which may besubstituted with an alkyl group, an aryl group and an acetyl group), anaryl group, a halogen atom and a cyano group.

An aryl group in the above substituted or unsubstituted aryl groupincludes, for example, a phenyl group and a naphthyl group. Thesubstituent includes, for example, a sulfonic acid group, a carboxylgroup, a phosphoric acid group, a hydroxyl group, an amino group (whichmay be substituted with an alkyl group, an aryl group and an acetylgroup), a ureido group, an alkyl group, an alkoxy group, a nitro group,a cyano group, a heterocyclic group and a halogen atom.

The above substituted or unsubstituted heterocyclic group is preferablya five-membered or six-membered ring, which may be further fused and maybe an aromatic heterocycle or a nonaromatic heterocycle. The heterocycleincludes, for example, pyridine, pyrazine, pyrimidine, pyridazine,triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine,quinoxaline, pyrrol, indole, furan, benzofuran, thiophene,benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole,benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole,pyrrolidine, piperidine, piperazine, imidazolidine and thiazoline. Theseheterocycles may have a substituent such as a sulfonic acid group, acarboxyl group, a phosphoric acid group, a hydroxyl group, an aminogroup (which may be substituted with an alkyl group, an aryl group or anacetyl group), a ureido group, an alkyl group, an alkoxy group, a nitrogroup, a cyano group and a halogen atom.

The above substituted or non-substituted alkenyl group includes a C₁₋₁₂alkenyl group. Examples of the substituent include a sulfonic acidgroup, a carboxyl group, a phosphoric acid group, a hydroxyl group,alkoxy group, an amino group (which may be substituted with an alkylgroup, an aryl group or an acetyl group), an aryl group, a halogen atomand a cyano group.

“A” in the above Formula (3) and Formula (X) represents a crosslinkinggroup. The crosslinking group usually includes a divalent hydrocarboncrosslinking group of, for example, 1 to 16 carbon atoms, preferably 1to 6 carbon atoms. Said crosslinking group includes, for example, analkylene, a cycloalkylene and an arylene group, and a group formed bycombining these groups, for example, a xylylene group. The crosslinkinggroup may be formed by combining with R₁₇ and R₁₈. The crosslinkinggroup may have a substituent, which includes, for example, a sulfonicacid group, a carboxyl group and a hydroxyl group.

The alkylene group includes, for example, an alkylene group of 1 to 16carbon atoms. A part of the carbon atoms of the alkylene group may besubstituted with a nitrogen, oxygen and sulfur atom. Also may beincluded a group formed by combination of an alkylene group and acycloalkylene group. An alkylene group of 1 to 4 carbon atoms ispreferable.

The cycloalkylene group includes, for example, a cycloalkylene group of1 to 16 carbon atoms. A part of the carbon atoms of the cycloalkylenegroup may be substituted with a nitrogen, oxygen and sulfur atom. Alsomay be included is a group formed by combination of an alkylene groupand a cycloalkylene group. The cycloalkylene group may be a hydrocarbonhaving a crosslinked ring or a hydrocarbon having a spiro ring.

The arylene group includes, for example, phenylene and naphthylenegroup, which may have a substituent. The substituent includes, forexample, a sulfonic acid group, a carboxyl group, a phosphoric acidgroup, a hydroxyl group, an amino group (which may be substituted withan alkyl group, an aryl group and an acetyl group), a ureido group, analkyl group, an alkoxy group, a nitro group, a cyano group and a halogenatom.

In the above Formula (3) and Formula (X), Y and Z represent eachindependently a halogen atom, a hydroxyl group, a sulfonic acid group, acarboxyl group, an amino group, a substituted or unsubstituted alkoxygroup, a substituted or unsubstituted cycloalkoxy group, a substitutedor unsubstituted aryloxyl group, a substituted or unsubstitutedheterocycloxyl group, a substituted or unsubstituted aralkyloxy group, asubstituted or unsubstituted alkenyloxy group, a substituted orunsubstituted alkylamino group, a substituted or unsubstituteddialkylamino group, a substituted or unsubstituted arylamino group, asubstituted or unsubstituted heterocyclic amino group, a substituted orunsubstituted aralkylamino group, a substituted or unsubstitutedalkenylamino group, a substituted or unsubstituted alkylthio group, asubstituted or unsubstituted arylthio, a substituted or unsubstitutedheterocyclic thio group and a substituted or unsubstituted alkenylthiogroup, provided that at least one of Y and Z has an ionic andhydrophilic group as a substituent. As the ionic and hydrophilic group,an anionic and hydrophilic group is preferable, including such as asulfonic acid group, a carboxyl group and a phosphoric acid. Amongthese, a sulfonic acid group or a carboxyl group is preferable, and asulfonic acid group is more preferable. The number of the ionic andhydrophilic groups contained in both of Y and Z is preferably 2 or more,usually 2 to 4 in total.

These ionic and hydrophilic groups may be a free form or an alkali metalsalt, an alkaline-earth metal salt, or an onium ion salt of an organicamine or an ammonium salt. The alkali metal includes, for example,sodium, potassium and lithium. The alkaline-earth metal includes, forexample, calcium and magnesium. The organic amine includes, for example,an alkylamine and an alkanolamine. The alkylamine includes, for example,a lower alkylamine of 1 to 4 carbon atoms such as methylamine andethylamine. The alkanolamine includes, for example, a mono-, di- ortri-C1-C4 lower alkanolamine such as monoethanolamine, diethanolamine,triethanolamine, monoisopropanolamine, diisopropanolamine andtriisopropanolamine. The preferable salt includes a salt of ammonium,sodium, potassium, lithium, monoethanolamine, diethanolamine,triethanolamine, monoisopropanolamine, diisopropanolamine andtriisopropanolamine. A salt of an alkali metal such as sodium or lithiumis usually used.

Preferable Y and Z are each independently a substituted or unsubstitutedamino groups. The substituted amino group is preferably an arylaminogroup that may have a substituent or an C1-C6 alkylamino group that mayhave a substituent. The arylamino group that may have a substituent ispreferably a phenylamino or naphthylamino group substituted with anionic and hydrophilic group. The C1-C6 alkylamino group that may have asubstituent is preferably a C1-C6 alkylamino group substituted with anionic and hydrophilic group. Said alkylamino group may be either a mono-or dialkylamino group, but is preferably a monoalkylamino group. A morepreferable combination of Y and Z is a case that one is an amino groupor a C1-C6 alkylamino group substituted with an ionic and hydrophilicgroup and the other is a phenylamino group or a naphthylamino groupsubstituted with an ionic and hydrophilic group. The ionic andhydrophilic group is preferably a sulfonic acid group or a carboxylgroup, more preferably a sulfonic acid group.

The above substituted or unsubstituted alkoxy group includes, forexample, an alkoxy group of 1 to 12 carbon atoms. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an alkoxy group, an amino group(which may be substituted with an alkyl group, an aryl group and anacetyl group), an aryl group, a halogen atom and a cyano group. Amongthese groups, a sulfonic acid group, a carboxyl group, a phosphoric acidgroup and a hydroxyl group are preferable.

The above substituted or unsubstituted cycloalkoxy group includes, forexample, a cycloalkoxy group of 1 to 12 carbon atoms. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an alkoxy group, an amino group(which may be substituted with an alkyl group, an aryl group and anacetyl group), an aryl group, a halogen atom and a cyano group. Amongthese groups, a sulfonic acid group, a carboxyl group, a phosphoric acidgroup and a hydroxyl group are preferable.

The above substituted or unsubstituted aryloxyl group includes, forexample, a phenoxyl group and a naphthoxyl group. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an amino group (which may besubstituted with an alkyl group, an aryl group and an acetyl group), aureido group, an alkyl group, an alkoxy group, a nitro group, a cyanogroup, a heterocyclic group and a halogen atom. Among these groups, asulfonic acid group, a carboxyl group, a phosphoric acid group and ahydroxyl group are preferable. The above substituted or unsubstitutedheterocyclic oxy group is preferably a five-membered or six-memberedring, which may further be fused and may be an aromatic heterocycle or anonaromatic heterocycle. The heterocycle includes, for example,pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline,isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrol,indole, furan, benzofuran, thiophene, benzothiophene, pyrazole,imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole,benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine,piperazine, imidazolidine and thiazoline. These heterocycles may have asubstituent such as a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an amino group (which may besubstituted with an alkyl group, an aryl group or an acetyl group), aureido group, an alkyl group, an alkoxy groups, a nitro group, a cyanogroup and a halogen atom.

The above substituted or unsubstituted aralkyloxy group includes, forexample, an aralkyloxy group of 1 to 12 carbon atoms. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an amino group (which may besubstituted with an alkyl group, an aryl group and an acetyl group), aureido group, an alkyl group, an alkoxy group, a nitro group, a cyanogroup, a heterocyclic group and a halogen atom. Among these groups, asulfonic acid group, a carboxyl group, a phosphoric acid group and ahydroxyl group are preferable.

The above substituted or unsubstituted alkenyloxy group includes, forexample, an alkenyloxy group of 1 to 12 carbon atoms. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an alkoxy group, an amino group(which may be substituted with an alkyl group, an aryl group and anacetyl group), an aryl group, a halogen atom and a cyano group. Amongthese groups, a sulfonic acid group, a carboxyl group, a phosphoric acidgroup and a hydroxyl group are preferable.

The above substituted or unsubstituted alkylamino group includes, forexample, an alkylamino group of 1 to 12 carbon atoms. The substituentincludes, for example, an ionic and hydrophilic group such as a sulfonicacid group, a carboxyl group or a phosphoric acid group; a hydroxylgroup, an alkoxy group, an amino group (which may be substituted with analkyl group, an aryl group and an acetyl group), an aryl group, ahalogen atom and a cyano group. Among these groups, a sulfonic acidgroup, a carboxyl group, a phosphoric acid group and a hydroxyl groupare preferable.

The above substituted or unsubstituted cycloalkylamino group includes,for example, a cycloalkylamino group of 1 to 12 carbon atoms. Thesubstituent includes, for example, a sulfonic acid group, a carboxylgroup, a phosphoric acid group, a hydroxyl group, an alkoxy group, anamino group (which may be substituted with an alkyl group, an aryl groupand an acetyl group), an aryl group, a halogen atom and a cyano group.Among these groups, a sulfonic acid group, a carboxyl group, aphosphoric acid group and a hydroxyl group are preferable.

The above substituted or unsubstituted arylamino group includes, forexample, an anilino group and a naphthylamino group. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an amino group (which may besubstituted with an alkyl group, an aryl group and an acetyl group), aureido group, an alkyl group, an alkoxy group, a nitro group, a cyanogroup, a heterocyclic group and a halogen atom. Among these groups, asulfonic acid group, a carboxyl group, a phosphoric acid group and ahydroxyl group are preferable.

The above substituted or unsubstituted heterocyclic amino group ispreferably a five-membered or six-membered ring, which may further befused and may be an aromatic heterocycle or a nonaromatic heterocycle.The heterocycle includes, for example, pyridine, pyrazine, pyrimidine,pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline,phthalazine, quinoxaline, pyrrol, indole, furan, benzofuran, thiophene,benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole,benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole,pyrrolidine, piperidine, piperazine, imidazolidine and thiazoline. Theseheterocycles may have a substituent, which includes, for example, asulfonic acid group, a carboxyl group, a phosphoric acid group, ahydroxyl group, an amino group (which may be substituted with an alkylgroup, an aryl group and an acetyl group), a ureido group, an alkylgroup, an alkoxy group, a nitro group, a cyano group and a halogen atom.

The above substituted or unsubstituted aralkylamino group includes, forexample, an aralkylamino group of 1 to 12 carbon atoms. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an amino group (which may besubstituted with an alkyl group, an aryl group and an acetyl group), aureido group, an alkyl group, an alkoxy group, a nitro group, a cyanogroup, a heterocyclic group and a halogen atom. Among these groups, asulfonic acid group, a carboxyl group, a phosphoric acid group and ahydroxyl group are preferable.

The above substituted or unsubstituted alkenylamino group includes, forexample, an alkenylamino group of 1 to 12 carbon atoms. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an alkoxy group, an amino group(which may be substituted with an alkyl group, an aryl group and anacetyl group), an aryl group, a halogen atom and a cyano group. Amongthese groups, a sulfonic acid group, a carboxyl group, a phosphoric acidgroup and a hydroxyl group are preferable.

The above substituted or unsubstituted alkylthio group includes, forexample, an alkylthio group of 1 to 12 carbon atoms. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an alkoxy group, an amino group(which may be substituted with an alkyl group, an aryl group and anacetyl group), an aryl group, a halogen atom and a cyano group. Amongthese groups, a sulfonic acid group, a carboxyl group, a phosphoric acidgroup and a hydroxyl group are preferable.

The above substituted or unsubstituted cycloalkylthio group includes,for example, a cycloalkylthio group of 1 to 12 carbon atoms. Thesubstituent includes, for example, a sulfonic acid group, a carboxylgroup, a phosphoric acid group, a hydroxyl group, an alkoxy group, anamino group (which may be substituted with an alkyl group, an aryl groupand an acetyl group), an aryl group, a halogen atom and a cyano group.Among these groups, a sulfonic acid group, a carboxyl group, aphosphoric acid group and a hydroxyl group are preferable.

The above substituted or unsubstituted arylthio group includes, forexample, a phenylthio group and a naphthylthio group. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an amino group (which may besubstituted with an alkyl group, an aryl group and an acetyl group), aureido group, an alkyl group, an alkoxy group, a nitro group, a cyanogroup, a heterocyclic group and a halogen atom. Among these groups, asulfonic acid group, a carboxyl group, a phosphoric acid group and ahydroxyl group are preferable.

The above substituted or unsubstituted heterocyclic thio group ispreferably a five-membered or six-membered ring, which may further befused and may be an aromatic heterocycle or a nonaromatic heterocycle.The heterocycle includes, for example, pyridine, pyrazine, pyrimidine,pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline,phthalazine, quinoxaline, pyrrol, indole, furan, benzofuran, thiophene,benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole,benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole,pyrrolidine, piperidine, piperazine, imidazolidine and thiazoline. Theseheterocycles may have a substituent, which includes, for example, asulfonic acid group, a carboxyl group, a phosphoric acid group, ahydroxyl group, an amino group (which may be substituted with an alkylgroup, an aryl group and an acetyl group), a ureido group, an alkylgroup, an alkoxy group, a nitro group, a cyano group and a halogen atom.

The above substituted or unsubstituted aralkylthio group includes, forexample, an aralkylthio group of 1 to 12 carbon atoms. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an amino group (which may besubstituted with an alkyl group, an aryl group and an acetyl group), aureido group, an alkyl group, an alkoxy group, a nitro group, a cyanogroup, a heterocyclic group and a halogen atom. Among these groups, asulfonic acid group, a carboxyl group, a phosphoric acid group and ahydroxyl group are preferable.

The above substituted or unsubstituted alkenylthio group includes, forexample, an alkenylthio group of 1 to 12 carbon atoms. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphoric acid group, a hydroxyl group, an alkoxy group, an amino group(which may be substituted with an alkyl group, an aryl group and anacetyl group), an aryl group, a halogen atom and a cyano group. Amongthese groups, a sulfonic acid group, a carboxyl group, a phosphoric acidgroup and a hydroxyl group are preferable.

In the above Formula (5), B represents an alkylene, an arylene or axylene group. The alkylene group includes, for example, an alkylenegroup of 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and morepreferably an ethylene group. The arylene group includes, for example,phenylene and naphthylene group, which may have a sustituent. Thesubstituent includes, for example, a sulfonic acid group, a carboxylgroup, a phosphoric acid group, a hydroxyl group, an amino group (whichmay be substituted with an alkyl group, an aryl group and an acetylgroup), a ureido group, an alkyl group, an alkoxy group, a nitro group,a cyano group, a heterocyclic group and a halogen atom.

In the above Formula (5), D and E represent each independently achlorine atom, a hydroxyl group, an amino group, an alkoxy group (whichmay be substituted with a substituent selected from a group consistingof a sulfonic acid group, a carboxyl group, a phosphoric acid group, adialkylamino group, an arylamino group, an acetylamino group, an alkoxygroup, an aryl group, a cyano group and a halogen atom), a phenoxylgroup (which may be substituted with one or not less than twosubstituents selected from a group consisting of a sulfonic acid group,a carboxyl group, a phosphoric acid group, a ureido group, an alkylgroup and an alkoxy group), a naphthoxyl group (which may be substitutedwith one or not less than two substituents selected from a groupconsisting of a sulfonic acid group and an acetylamino group), abenzyloxyl group (which may be substituted with a sulfonic acid group),a phenethyloxyl group (which may be substituted with a sulfonic acidgroup), an alkylamino group (which may be substituted with a substituentselected from a group consisting of a sulfonic acid group, a carboxylgroup, a phosphoric acid group, a hydroxyl group, an alkoxy group, adialkylamino group, an arylamino group, an aryl group, a halogen atomand a cyano group), an anilino group (which may be substituted with oneor not less than two substituents selected from a group consisting of asulfonic acid group, a carboxyl group, a phosphoric acid group, ahydroxyl group, a dialkylamino group, an arylamino group, an acetylaminogroup, a ureido group, an alkyl group, an alkoxy group, a nitro group, acyano group, a heterocyclic group and a halogen atom), a naphthylaminogroup (which may be substituted with a sulfonic acid group or a hydroxylgroup), a benzylamino group (which may be substituted with a sulfonicacid group), a phenethylamino group (which may be substituted with asulfonic acid group), an alkylthio group (which may be substituted witha sulfonic acid group, a carboxyl group or a hydroxyl group) and anarylthio group (which may be substituted with one or not less than twosubstituents selected from a group consisting of a sulfonic acid group,a carboxyl group, a hydroxyl group and an alkyl group). At least one ofD and E is a group having an ionic and hydrophilic group as asubstituent.

Preferable D and E are each independently substituted or unsubstitutedamino groups. The substituted amino group is preferably an arylaminogroup that may have a substituent or an C1-C6 alkylamino group that mayhave a substituent. The arylamino group that may have a substituent ispreferably a phenylamino group or a naphthylamino group that issubstituted with an ionic and hydrophilic group. The C1-C6 alkylaminogroup that may have a substituent is preferably a C1-C6 alkylamino groupthat is substituted with an ionic and hydrophilic group. Said alkylaminogroup may be either a mono- or dialkylamino group, but is preferably amonoalkylamino group. A more preferable combination of Y and Z is thecase that one is an amino group or a C1-C6 alkylamino group substitutedwith an ionic and hydrophilic group and the other is a phenylamino ornaphthylamino group substituted with an ionic and hydrophilic group. Theionic and hydrophilic group is preferably a sulfonic acid group, acarboxyl group or a hydroxyl group, and more preferably a sulfonic acidgroup.

Specific examples of combinations of a metal (M) in a metallic compoundand an organic amine to be used for producing a phthalocyanine colorantof the present invention are shown in Tables 1 to 7, but are not limitedto the following examples. In the Tables, an organic amine is shown in afree acid form. TABLE 1 No. M

1 Cu

2 Cu

3 Cu

4 Cu

5 Cu

6 Cu

7 Cu

TABLE 2 No. M

8 Cu

9 Cu

10 Cu

11 Cu

12 Cu

13 Cu

14 Cu

TABLE 3 No. M

15 Cu

16 Cu

17 Cu

18 Cu

19 Cu

20 Cu

TABLE 4 No. M

21 Cu

22 Cu

23 Cu

24 Cu

25 Cu

26 Cu

27 Cu

TABLE 5 No. M

28 Cu

29 Cu

30 Cu

31 Cu

32 Cu

33 Cu

TABLE 6 No. M

34 Cu

35 Cu

36 Cu

37 Cu

38 Cu

39 Cu

TABLE 7 No. M

40 Cu

41 Cu

42 Ni

43 Ni

44 Zn

45 Zn

46 AlOH

47 AlOH

A phthalocyanine colorant of the present invention is obtained bysubjecting 4-sulfophthalic acid derivatives to reaction with themselvesor subjecting a 4-sulfophthalic acid derivative to reaction with aphthalic acid (phthalic anhydride) derivative in the presence of ametallic compound to obtain a compound (sulfophthalocyanine of asubstitution type at β-position), followed by reaction of this productwith a chlorination agent to convert a sulfonic acid group to achlorosulfonyl group and further reaction with an amidation agent and anorganic amine. 4-Sulfophthalic acid derivative used as a raw materialusually contains, as impurities, about 15 to 25% by weight of compoundssulfonated in the 3-position and thus compounds substituted at theα-position, derived from such compounds, are mixed in an objectivephthalocyanine colorant. To further enhance effects of the presentinvention (particularly to obtain an ink with higher ozone fastness), itis preferable to use a raw material containing less impuritiessulfonated at the 3-position.

Also in an objective phthalocyanine colorant, compounds formed bydecomposition of a part of chlorosulfonyl groups during the reaction aremixed in the reaction product, however, they are not particularly anobstacle. Thus obtained colorant is represented by Formula (14) as shownbelow and will contain a derivative substituted at the β-position, as amain component, of at least not less than 60%, preferably not less than70% and more preferably not less than 75%:

(In Formula (14), M, R₁₇ and R₁₈ represent each the same meaning asdefined above; 1 includes 0 and is less than 1, preferably not more than0.7, more preferably not more than 0.5 and most preferably not more than0.3; n is not less than 0.3 and preferably not less than 0.7 and notmore than 3; m is not less than 1 and not more than 3.7; and the totalof l, m and n is not less than 2 and not more than 4; and the values ofl, m and n show each an average value in a mixture.)

In producing a phthalocyanine colorant of the present invention, it ispreferable to adopt ratio (mole ratio) of an amidation agent to anorganic amine represented by Formula (X) such that ratio of anunsubstituted sulfamoyl group to a substituted sulfamoyl group in saidphthalocyanine colorant falls in the range of 1:3 to 3:1. High ratio ofan unsubstituted sulfamoyl group (high reaction ratio of an amidationagent) gives high ozone fastness of a recorded image by an inkcontaining thus obtained phthalocyanine colorant, while the coloranttends to have low water-solubility and cause bronze phenomenon. Incontrast, high ratio of an organic amine gives high water-solubility ofthus obtained phthalocyanine colorant, causing little bronze phenomenon,while low ozone fastness of an image. Therefore, in response to the kindof an organic amine to be used that is represented by Formula (X), ratioof the amidation agent and the organic amine can be adjusted, asappropriate, to obtain good balance.

A method for producing a compound of the present invention representedby Formula (1) will be described.

At first, a metallo phthalocyanine sulfonic acid represented by theabove Formula (6) is synthesized. As described above, a compoundsubstituted at the α-position, derived from raw materials is formed as abyproduct in the production of a phthalocyanine colorant of the presentinvention, but the production method is described here in reference to acompound substituted at the β-position, that is, a main component. Ametallo phthalocyanine sulfonic acid represented by Formula (6) can besynthesized, for example, by subjecting 4-sulfophthalic acid derivativesto reacting themselves or subjecting a 4-sulfophthalic acid derivativeto reaction with a phthalic acid (phthalic anhydride) derivative in thepresence of a catalyst and a metallic compound. By changing reaction molratio of a 4-sulfophthalic acid derivative to a phthalic acid (phthalicanhydride) derivative, the number of sulfonyl groups, that is, values ofa to d in the Formula can be adjusted. The 4-sulfophthalic acidderivative includes 4-sulfophthalic acid, 4-sulfophthalic anhydride,4-sulfophthalimide, 4-sulfophthalonitrile, 4- or5-sulfo-2-cyanobenzamide, 5-sulfo-1,3-diiminoisoindolin or saltsthereof. Among these compounds, 4-sulfophthalic acid or a salt thereofis usually preferable. When phthalic acid, phthalic anhydride andphthalimide are used, the addition of urea is essential. Use amount ofthe urea is 5 to 100 times mol based on 1 mol of a 4-sulfophthalic acidderivative.

(In Formula (6), M, L, a, b, c and d represent each the same meaning asabove.)

The reaction is usually carried out in the presence of a solvent. Anorganic solvent of boiling point not lower than 100° C., preferably notlower than 130° C. is used, which includes, for example, n-amyl alcohol,n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 1-octanol,2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol,trichlorobenzene, chloronaphthalene, nitrobenzene, quinoline, sulfolaneand urea. Use amount of the solvent is 1 to 100 times by mass of that ofa 4-sulfophthalic acid derivative.

The catalyst includes 1,8-diazabicyclo[5,4,0]-7-undecene, ammoniummolybdate and boric acid. Amount of the addition is 0.001 to 1 mol basedon 1 mol of a 4-sulfophthalic acid derivative.

The metallic compound includes a halide, a carboxylate, a sulfate, anitrate, an acetylacetonate, a carbonyl compound, a complex, and thelike of such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co,Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge,Sn, Pb, Sb and Bi. For example, copper chloride, copper bromide, nickelchloride, nickel acetate, cobalt chloride, cobalt acetate and cobaltacetylacetonate are included. Use amount of the metallic compound is0.15 to 0.35 times mol based on 1 mol of 4-sulfophthalic acidderivatives or 1 mole of total of a 4-sulfophthalic acid derivative andan (unsubstituted) phthalic acid derivative.

Reaction temperature is usually 100 to 290° C. and preferably 130 to270° C. Reaction times depend on reaction temperature, but are usually 1to 8 hours. Phthalocyanine sulfonic acid or a salt form thereof isobtained by filtration, salting out (or acid depositing) and dryingafter completion of the reaction. When a free acid is desired, forexample, the reaction product is precipitated using an acid. When a saltis desired, the reaction product is salted out. When a desired salt isnot obtained by salting out, for example, an ordinary method for saltexchanging, where a desired organic or inorganic base is added to thefree acid obtained, can be used.

Copper phthalocyanine sulfonic acid or a salt thereof in the aboveFormula (6), where M is copper, is synthesized by a method described inLiterature 8. Copper phthalocyanine sulfonic acid in the above Formula(6), where a, b, c and d are each 1, is obtained by reacting4-sulfophthalic acid (1 mol), copper chloride (II) (0.3 mol), ammoniumphosphomolybdate (0.003 mol), urea (6 mol) and ammonium chloride (0.5mol) at 180° C. for 6 hours in a sulfolane solvent, however, asreactivity depends on the kinds and use amount of a 4-sulfophthalic acidderivative, a metallic compound, a solvent, a catalyst, and the like,and reaction conditions are not limited to the above.

By subjecting phthalocyanine sulfonic acid or a salt thereof representedby Formula (6) to reaction with a chlorination agent in a solvent suchas an organic solvent, sulfuric acid, fuming sulfuric acid orchlorosulfonic acid, phthalocyanine sulfonyl chloride represented byFormula (8) is obtained. The chlorination agent is preferably used inexcess to a sulfonic acid group of phthalocyanine sulfonic acid or asalt thereof, and is about 1 to 10 times, preferably not less than 1.5times, as mole ratio of the chlorination agent to the sulfonic acidgroup. The organic solvent to be used in the reaction includes, but isnot limited to, such as benzene, toluene, nitrobenzene, chlorobenzene,N,N-dimethylformamide and N,N-dimethylacetoamide. The chlorination agentincludes, but is not limited to, such as chlorosulfonic acid, thionylchloride, sulfuryl chloride, phosphorus trichloride, phosphoruspentachloride and phosphorus oxychloride. With regard to aphthalocyanine colorant of the present invention, impurities may beformed by chlorination of a phthalocyanine nucleus and mixed in thereaction product.

(wherein M, a, b, c and d represent each the same meaning as above.)

Thus obtained phthalocyanine sulfonyl chloride is then reacted with anorganic amine corresponding to an amidation agent and represented byFormula (X) as shown below in water solvent usually at pH 6 to 10,usually at 5 to 70° C. and usually for 1 to 20 hours to obtain anobjective compound. The total use amount (mole ratio) of an amidationagent and the above organic amine is preferably not less than theequimolar ratio to the sulfonyl chloride group of the abovephthalocyanine sulfonyl chloride, usually 1 to 20 times by mole andpreferably 1.5 to 5 times by mole. The use ratio of the above organicamine may be decided according to the ratio of substituted sulfamoylgroups of the objective compound.

An amidation agent to be used in the reaction, which is an agent forintroducing an —NH₂ group, includes, but is not limited to, for example,an ammonium salt such as ammonium chloride and ammonium sulfate; urea,ammonia water and ammonia gas.

(In Formula (X), R₁₇, R₁₈, A, Y and Z represent each the same meaning asabove.)

Use amount of the organic amine is usually not less than the theoreticalvalue based on 1 mol of a phthalcyanine compound. The amount has not theupper limit, but is not more than 10 times by mole from economicalstandpoint. The amount depends on reactivity of an organic amine andreaction conditions and is not limited to the above amount.

A method for producing a corresponding organic amine represented byFormula (X) will be described. For example, amines, alcohols or thiols,corresponding to Y, of usually 0.95 to 1.1 mol and2,4,6-trichloro-5-triazin (cyanuric chloride) of 1 mol are reacted inwater usually at pH 3 to 7, usually at 5 to 40° C. and usually for 2 to12 hours to obtain a primary condensate. Next, amines, alcohols orthiols corresponding to Z of usually 0.95 to 1.1 mol are reacted usuallyat pH 4 to 10, usually at 5 to 80° C. and usually for 0.5 to 12 hours toobtain a secondary condensate. After that, diamines, corresponding to acrosslinking group, of 1 to 50 mol are reacted usually at pH 9 to 12,usually at 5 to 90° C. and usually for 0.5 to 8 hours to obtain acompound represented by the above Formula (X). Order of condensation canbe determined, as appropriate, according to reactivity of each compoundand is not limited to the above. With regard to a phthalocyaninecolorant of the present invention, a dimer (for example, Pc-L-Pc) or atrimer of a phthalocyanine ring (Pc) linked through a divalent bondinggroup (L) may be formed and mixed in the reaction product as impurities,wherein the divalent bonding groups (L) present in multiple may be sameor different.

The divalent bonding group represented by L includes a sulfonyl group(—SO₂—) and —SO₂—NH—SO₂— and the like. The bonding group may also be agroup formed by combining these groups.

Thus obtained phthalocyanine colorant of the present invention can beseparated by filtration, and the like, after precipitation with acid orsalt out. Salt out is preferably carried out in, for example, acidic toalkaline conditions, preferably in a range of pH 1 to 11. Temperature insalt out is not limited especially, however, salt out is preferablycarried out by adding a salt, and the like after heating usually at 40to 80° C., preferably 50 to 70° C.

A phthalocyanine colorant of the present invention that is synthesizedby the above method and represented by the above Formula (1) is obtainedin a form of a free acid or a salt thereof. When a free acid is desired,the reaction product is precipitated using an acid. When a salt isdesired, the reaction product is salted out. When a desired salt is notobtained by salting out, for example, an ordinary method for saltexchanging, where a desired organic or inorganic base is added to thefree acid, can be used.

A cyan ink of the present invention contains a phthalocyanine colorantof the above Formula (1) produced by the above method and is preparedusing water as a medium, and when the ink is used as an ink for ink-jetrecording, the phthalocyanine colorant with lower content of an anionsuch as Cl⁻ and SO₄ ²⁻ is preferable, and general standard of the totalcontent of Cl⁻ and SO₄ ²⁻ is not higher than 5% by weight, preferablynot higher than 3% by weight and more preferably not higher than 1% byweight in the phthalocyanine colorant, while not higher than 1% byweight in the ink. To produce a phthalocyanine colorant of the presentinvention having lower Cl⁻ and SO₄ ²⁻, a method for desalting can beapplied using, for example, an ordinary method using a reverse osmosismembrane or a method for subjecting a dried solid or a wet cake of aphthalocyanine colorant of the present invention to stirring in a mixedsolvent of an alcohol and water, followed by filtering and drying. Analcohol to be used is a lower alcohol of 1 to 4 carbon atoms, preferably1 to 3 carbon atoms and more preferably methanol, ethanol or 2-propanol.In desalting using an alcohol, a method for desalting by heating thealcohol to near boiling point thereof and then cooling can also beadopted. The content of Cl⁻ and SO₄ ⁻ is measured by, for example, anion chromatography.

In using a cyan ink of the present invention as an ink for ink-jetrecording, it is preferable to use a phthalocyanine colorant having alower content of a heavy metal (ion) such as zinc and iron and a metal(cation) such as calcium and silica {except a metal (M in Formula (1))contained in phthalocyanine skeleton}. A general standard content in apurified and dried phthalocyanine colorant is, for example, not higherthan about 500 ppm for each heavy metal (ion) such as zinc and iron anda metal (cation) such as calcium and silica. The content of a heavymetal (ion) and a metal (cation) is measured by an ion chromatography,an atomic absorption analysis or an ICP (Inductively Coupled Plasma)emission analysis.

An ink of the present invention contains 0.1 to 8% by mass, preferably0.3 to 6% by mass of a phthalocyanine colorant of the above Formula (1).An ink of a lower concentration type contains 0.1 to 2.5% by mass of aphthalocyanine compound of the present invention.

An ink of the present invention is prepared using water as a medium. Anink of the present invention contains 0.3 to 6% by mass of a mixture ofa compound of the above Formula (1) obtained as above and has the aboveconditions or a salt thereof. An ink of the present invention furthercontains a water-soluble organic solvent, as needed, within the contentrange not impairing an effect of the present invention. A water-solubleorganic solvent is used as a dye-dissolving agent, an agent forprohibiting dryness (a wetting agent), a viscosity modifier, apenetration promoter, a surface tension modifier, an antifoaming agent,and the like. Other ink modifiers include known additives such as anantiseptics and fungicide, a pH controller, a chelate agent, an rustpreventive, an ultraviolet absorber, a viscosity modifier, adye-dissolving agent, a fading inhibitor, an emulsion stabilizer, asurface tension modifier, an antifoaming agent, a dispersing agent and adispersion stabilizer. Content of a water-soluble organic solvent is 0to 60% by weight, preferably 10 to 50% by weight based on the totalamount of an ink. An ink modifier is preferably used in 0 to 20% byweight, preferably 0 to 15% by weight based on the total amount of anink. The remainder other than the above is water. A water-solubleorganic solvent that can be used in the present invention includes, forexample, C₁₋₄ alkanols such as methanol, ethanol, n-propanol,isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol;carboxamides such as N,N-dimethyl formamide and N,N-dimethyl acetamide;heterocycle ketones such as 2-pyrrolidone, N-methyl-2-pyrrolidone,1,3-dimethylmidazolidin-2-one and 1,3-dimethylhexahydropyrimid-2-one;ketones or keto-alocohols such as acetone, methyl ethyl ketone and2-methyl-2-hydroxypentane-4-one; cyclic ethers such as tetrahydrofuranand dioxane; monomers or oligomers or polyalkylene glycols having (C₂₋₆)alkylene unit such as ethylene glycol, 1,2- or 1,3-propylene glycol,1,2- or 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, dipropylene glycol,thiodiglycol, polyethylene glycol and polypropylene glycol;polyol(triol) such as thioglycol, glycerine and hexane-1,2,6-triol;alkyl ethers of polyhydric alcohols such as ethylene glycol monomethylether, ethylene glycol monoethyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether, triethylene glycol monomethylether and triethylene glycol monoethyl ether; γ-butyrolactone anddimethylsulfoxide.

In an ink according to the present invention, a preferable water-solubleorganic solvent includes a mono- or polyhydric alcohol having carbonatoms of 3 to 8, and 2-pyrrolidone which may have a substituent of analkyl group having carbon atoms of 1 to 3, and the like, and as apolyhydric alcohol, one having 2 to 3 hydroxyl groups is preferable.Typically, isopropanol, glycerine, mono, di- or triethylene glycol,dipropylene glycol, 2-pyrrolidone and N-methyl-2-pyrrolidone, butanol,and the like are included and isopropanol, glycerine, diethylene glycoland 2-pyrrolidone are more preferable. These water-soluble organicsolvents are used alone or in combination.

An antiseptics and fungicide include organosulfur type, organonitrogensulfur type, organohalogen type, haloarylsulfone type, iodopropargyltype, N-haloalkylthio type, benzthiazole type, nitrile type, pyridinetype, 8-hydroxyquinoline, isothiazoline type, dithiol type, pyridineoxide type, nitropropane type, organotin type, phenol type, quaternaryammonium salt type, triazine type, thiadiazine type, anilide type,adamantane type, dithiocarbamate type, brominated indanone type,benzylbromacetate type, inorganic salts, etc. An organohalo typecompounds include, for example, sodium pentachlorophenolate, andpyridine oxide type compounds include, for example,2-pyridinethiol-1-oxide sodium salt, and inorganic salt type compoundsinclude, for example, anhydrous sodium acetate, and isothiazoline typecompounds include, for example, 1,2-benzisothiazoline-3-one,2-n-octyl-4-isothiazoline-3-one,5-chloro-2-methyl-4-isothiazoline-3-one,5-chloro-2-methyl-4-isothiazoline-3-one magnesium chloride,5-chloro-2-methyl-4-isothiazoline-3-one calcium chloride and2-methyl-4-isothiazoline-3-one calcium chloride, and the like. Otherantiseptics and fungicide includes sodium sorbate, sodium benzoate, andthe like (for example, Proxcel GXL(S) (trade name)) and ProxcelXL-2(S)(trade name), and the like manufactured by Abesia Co., Ltd.).

As for a pH adjustor, any substance can be used as far as it can controlpH of an ink within the range of 6.0 to 11.0 to improve storagestability of an ink. For example, alkanolamines such as diethanolamineand triethanolamine; alkali metal hydroxides such as lithium hydroxide,sodium hydroxide, potassium hydroxide and ammonium hydroxide; and alkalimetal carbonates such as lithium carbonate, sodium carbonate andpotassium carbonate are included.

Chelate agents include, for example, sodium ethylendiaminetetraacetate,sodium nitrilotriacetate, sodium hydroxyethylethylenediamine triacetate,sodium diethylenetriamine pentaacetate, sodium uramildiacetate, etc.Rust preventives include, for example, acidic sulfite, sodiumthiosulfate, ammonium thioglycolate, diisopropylammonium nitrite,pentaerithritol tetranitrate, dicyclohexylammonium nitrite, etc.

An ultraviolet absorber, for example, a benzophenone type compound, abenzotriazole type compound, a cinnamic acid type compound, a triazinetype compound, a stilbene type compound, or a compound which emitsfluorescence by absorbing ultraviolet rays, represented by a benzoxazoletype compound, a so-called fluorescent brightening agent can also beused.

As a viscosity modifier, a water soluble polymer compound is exemplifiedbesides a water soluble organic solvent including, for example,polyvinyl alcohol, cellulose derivatives, polyamine, polyimine, and thelike.

A dye solubilizer includes, for example, urea, e-caprolactam, ethylenecarbonate, and the like.

An fading inhibitor is used to improve image storage ability. As thediscoloration inhibitor, various kinds of an organic series or a metalcomplex series discoloration inhibitor can be used. Organic fadinginhibitors include, for example, hydroquinones, alkoxyphenols,dialkoxyphenols, phenols, anilines, amines, indanes, chromans,alkoxyanilines and heterocycles. Metal complexes include nickel complex,zinc complex, etc.

A surface tension modifier includes surfactants such as anionicsurfactants, amphoteric surfactants, cationic surfactants and nonionicsurfactants. Anionic surfactants include salts such asalkylsulfocarboxylate, α-olefinsulfonate, polyoxyethylene-alkyletheracetate, N-acylamino acids and their salts, N-acyl-methyltaurine salts,alkylsulfate polyoxyalkylethersulfate, alkylsulfatepolyoxyethylenealkyletherphosphate, rosin acid soap, castor oil sulfate,lauryl alcohol sulfate, alkylaryl sulfonate, diethyl sulfosuccinate,diethylhexyl sulfosuccinate, dioctyl sulfosuccinate, along with esterssuch as alkylphenol phosphate and alkyl phosphate; cationic surfactantsinclude 2-vinylpyridine derivatives and poly(4-vinylpyridine)derivatives. Amphoteric surfactants include lauryldimethylaminoaceticacid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine,palm oil fatty acid amide propyl dimethylamino acetic acid betaine,polyoctylpolyaminoethyl glycine and other imidazolidine derivatives.Nonionic surfactants include ethers such as polyoxyethylene nonylphenylether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenylether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether,polyoxyethylene alkyl ethers and polyoxyethylene aryl alkyl ether;esters such as polyoxyethylene oleic acid, polyoxyethylene oleate,polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate,sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleateand polyoxyethylene stearate; acetylene glycols such as2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3,6-dimethyl-4-octyn-3,6-diol and3,5-dimethyl-1-hexyn-3-ol (for example, Surfinol-104, -82, -465,Olfin-STG manufactured by Nisshin Chem Co., Ltd.)

These ink modifiers are used alone or in combination. In thisconnection, surface tension of an ink according to the present inventionis usually 25 to 70 mN/m, more preferably 25 to 60 mN/m. And a viscosityof an ink according to the present invention is preferably not higherthan 30 mPa·s. Further, it is more preferable to adjust it to not higherthan 20 mPa·s.

As an antifoaming agent, a fluorine-based or a silicone-based compoundis used, if necessary.

On producing an ink according to the present invention, order ofdissolving each agent is not limited in particular. In preparation of anink, water used is preferably such one as contains low impurities, suchas ion-exchanged water or distilled water. Further, foreign matters maybe removed by microfiltration with a membrane filter, and the like, ifnecessary, and in case of using it as an ink for an ink-jet printer,conducting microfiltration is preferable. A pore diameter inmicrofiltration is usually 1 micrometer to 0.1 micrometer, preferably0.8 micrometer to 0.2 micrometer.

An ink according to the present invention can be used not only formonochrome image formation, but also for full-colored image formation.For full-colored image formation, it is also used as an ink set togetherwith a magenta ink, yellow ink, and black ink. Further, to form an imagewith high resolution, it is also used as an ink set together with alight magenta ink, blue ink, green ink, orange ink, dark yellow ink,grey ink, and the like.

As a colorant applicable to a yellow ink, various types can be used. Forexample, it includes aryl or heterylazo dyes having phenols, naphthols,anilines, heterocyclics such as pyrazolone and pyridone, and open chaintype active methylene compounds as a bonding component (hereinaftercalled as a coupler component); azomethine dyes having open chain typeactive methylene compounds as a coupler component; methine dyes such asbenzylidene dyes, monomethine oxonol dyes, and the like; quinone typedyes such as naphthoquinone dyes, anthraquinone dyes, and the like; andas other types of dyes, quinophthalone dyes, nitro-nitroso dyes,acridine dyes, acridinon dyes, and the like.

As a colorant applicable to a magenta ink, various types can be used.For example, it includes arylazo dyes having phenols, naphthols,anilines as a coupler component; azomethine dyes having pyrazolones andpyrazolotriazoles as a coupler component; methine dyes such as arylidenedyes, styryl dyes, merocyanine dyes, cyanine dyes, oxonol dyes, and thelike; carbonium dyes such as diphenylmethane dyes, triphenylmethanedyes, and xanthene dyes; quinone dyes such as naphthoquinone dyes,anthraquinone dyes, and anthrapyridone dyes; and fused polycyclic dyessuch as dioxazine dyes; and the like.

Each colorant described above may exhibit each color of yellow, magentaand cyan for the first time after a part of chromophores is dissociated,and in that case, a counter cation may be an inorganic cation of such asan alkali metal or ammonium, or an organic cation such as pyridinium anda tertiary ammonium salt, and further a polymer cation which has theseas partial structure thereof. As a black colorant applicable, adispersion of carbon black can be exemplified besides disazo, trisazoand tetraazo dyes.

An ink according to the present invention can be used in a recordingmethod such as in printing, duplication, marking, writing, drafting,stamping, and the like, and particularly is suitable for use in ink-jetprinting.

An ink-jet recording method according to the present invention affordsenergy to an ink prepared as described above, and form an image on knownimage accepting materials, namely a plain paper, a resin-coated paper, aprofessional paper for an ink-jet, a Glossy paper, a Glossy film, apaper commonly used for electronic photography, a fiber or a cloth(cellulose, nylon, wool, and the like), glass, metal, pottery, leather,and the like.

On forming an image, to furnish gloss or water fastness, or to improveweather fastness, dispersed materials of polymer particulates (also saidas polymer latex) may be used together. As for a period during whichpolymer latex is furnished to a recording material, it may be before,after, or at the same time of providing a colorant, and accordingly alsoa place of the addition thereof may be in a recording material, or in anink, or it may be used as a liquid material of a polymer latex alone.

Hereinafter is explained, a recording material (especially, a recordingpaper and a recording film) used for ink-jet printing using an inkaccording to the present invention. A backing material in a recordingpaper and a recording film consists of a chemical pulp such as LBKP,NBKP, and the like; a mechanical pulp such as GP, PGW, RMP, TMP, CTMP,CMP, CGP, and the like; a waste paper pulp such as DIP, and the like;and those produced using various types of apparatus such as Fourdriniermachine, cylinder paper machine, and the like after mixing additives, ifnecessary, such as a pigment, a binder, a sizing agent, a fasteningagent, a cationic agent, a strengthening agent for paper, and the like,can be used. In addition to these backing materials, a synthetic paperand a plastic film and sheet may be used, and backing material thicknessis preferably 10 to 250 μm, and basis weight is desirably 10 to 250g/m². The backing material may be provided with an ink receiving layerand a back coating layer as it is, or may be provided with an inkreceiving layer and a back coating layer after it is provided with asize press or an anchor coat layer with starch or polyvinyl alcohol.Further, the backing material may be subjected to treatment forsmoothing with a calendering device such as a machine calender, a TGcalender, a soft calender, and the like. In the present invention, as abacking material, a paper laminated with a polyolefin (for example,polyethylene, polystyrene, polyethylene terephthalate, polybutene, and acopolymer thereof) at both surfaces and a plastic film are preferablyused. Into a polyolefin, white pigments (for example, titanium oxide,zinc oxide) or toning dyes (for example, cobalt blue, ultramarine blue,neodymium oxide) are preferably added.

In the ink receiving layer provided on the backing material, a pigmentor a water-based binder may be contained. As the pigment, a whitepigment is preferable, including a white inorganic pigment such ascalcium carbonate, kaolin, talc, clay, diatomaceous earth, syntheticamorphous silica, aluminum silicate, magnesium silicate, calciumsilicate, aluminum hydroxide, alumina, lithopone, zeolite, bariumsulfate, calcium sulfate, titanium dioxide, zinc sulfide, zinccarbonate, and the like; and an organic pigment such as a styrene basedpigment, an acrylonitrile based pigment, a urea resin, a melamine resin,and the like. As a white pigment contained in the ink receiving layer, aporous inorganic pigment is preferable, in particular, syntheticamorphous silica having large pore area, and the like are suitable. Asthe synthetic amorphous silica, a silicic anhydride obtained by a dryproduction method, and a water-containing silicic acid obtained by a wetproduction method, can be used, and it is particularly desirable to usea water-containing silicic acid.

As the water-based binder contained in the ink receiving layer, awater-soluble polymer such as polyvinyl alcohol, silanol modifiedpolyvinyl alcohol, starch, cation type starch, casein, gelatin,carboxylmethyl cellulose, hydroxylethyl cellulose, polyvinylpyrrolidone, a polyalkylene oxide, derivatives of a polyalkylene oxide,and the like, and a water-dispersible polymer such as styrene-butadienelatex, acrylonitrile based emulsion, and the like, are exemplified.These water-based binders can be used alone or in combination with atleast two kinds thereof. In the present invention, among these,especially polyvinyl alcohol and silanol modified polyvinyl alcohol aresuitable from the points of adhesion property to a pigment, andresistance to peeling-off of an ink receiving layer. The ink receivinglayer can contain, besides a pigment and a water-based bonding agent, amordant, a water fastness modifier, a light fastness improver, asurfactant, and other additives.

As a mordant added in an ink receiving layer, for example, a polymermordant is used.

A water fastness modifier is effective for modifying water fastness ofan image, and as the water fastness modifier, a cationic resin isdesirable, in particular. Such a cationic resin includes polyamidepolyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, apolymer of dimethyl diallyl ammonium chloride, cationic polyacrylamide,a colloidal silica, and the like, and among these cationic resins,particularly polyamide polyamine epichlorohydrin is suitable. Content ofthese cationic resins is preferably 1 to 15% by weight, particularlypreferably 3 to 10% by weight, based on the total solid portion in anink receiving layer.

The light fastness improver includes zinc sulfate, zinc oxide, ahindered amine type antioxidant, an ultra violet light absorber such asa benzophenone type and a benzotriazole type absorber, and the like.Among these, zinc sulfate is suitable.

A surfactant functions as a coating coagent, a peel improver, a slideimprover, or an antistatic agent. Instead of a surfactant, an organicfluorocompound may be used. A hydrophobic organic fluorocompound ispreferable. Examples of the organic fluorocompound include afluorine-based surfactant, an oily state fluorine-based compound (forexample, a fluoro-oil), and a solid state fluorocompound resin (forexample, a tetrafluoroethylene resin).

As the other additives added in an ink receiving layer, a pigmentdispersing agent, a thickener, an antifoaming agent, dyes, a fluorescentwhitener, a preservative, a pH adjustor, a matting agent, a hardener,and the like are exemplified. In this connection, the ink receivinglayer may be one layer or two layers.

On a recording paper and a recording film, a back coating layer may beprovided, and as a component possible to be added in this layer, a whitepigment, a water-based binder, and other components are exemplified.White pigments contained in a backcoat layer includes, for example,white inorganic pigments such as precipitated calcium carbonate, groundcalcium carbonate, kaline, talc, calcium sulfate, barium sulfate, titandioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white,aluminium silicate, diatomite, calcium silicate, magnesium silicate,synthetic amorphous silica, colloidal silica, colloidal alumina,pseudo-boehmite, aluminium hydroxide, alumina, lithopone, zeolite,hydrated halloysite, magnesium carbonate and magnesium hydroxide; andorganic pigments such as styrenic plastic pigments, acrylic plasticpigments, polyethylene, microcapsule, a urea-resin and a melanin-resin.

A water-based binder contained in a backcoat layer includepoly(styrene-co-maleate salt), poly(styrene-co-acrylate salt);water-soluble polymers such as polyvinyl alcohol, silanol modifiedpolyvinyl alcohol, starch, cationic starch, casein, gelatin,carboxymehthylcellulose, hydroxyehthylcellulose andpolyvinylpyrrolidone; and water dispersible polymers such asstyrene-butadiene latex, acrylic emulsion, etc. The other componentscontained in the back coating layer includes an antifoaming agent, afoam inhibiting agent, dyes, a fluorescent whitener, antiseptics, awater fastness modifier, and the like.

In a composing layer of an ink-jet recording paper and a recording film(containing a back coating layer), polymer latex may be added. Thepolymer latex is used to improve physical properties of a membrane suchas for dimensional stabilization, curling prevention, adhesionprevention, and crazing prevention of a membrane. When polymer latexhaving low glass transition temperature (of not higher than 40° C.) isadded in a layer containing a mordant, crazing or curling of the layercan be prevented. Moreover, when polymer latex having high glasstransition temperature is added in a back coated layer, curling of thelayer can also be prevented.

These recording papers and recording films are generally called as aprofessional paper for an ink-jet, a Glossy paper or a Glossy film, andthey are commercially sold, for example, as Pictoriko (trade name:manufactured by Asahi Glass Co. Ltd.), Color BJ Paper, Exclusive UsePaper for High Grade, Color BJ Photofilm Sheet, Super Photopaper,Professional Photopaper (all of these are trade names: manufactured byCanon Inc.), Paper for Color Image Jet (trade name: manufactured bySharp Corporation.), Paper for PM Photo, Glossy Film Exclusive for SuperFine Use (all of these are trade names: manufactured by Epson Co.,Ltd.), PictaFine (trade name: manufactured by Hitachi Maxell, Ltd.), andthe like. Especially, an ink-jet recording method using an ink accordingto the present invention functions particularly effectively on arecording paper and a recording film having an image receiving layerwith an ink, which layer, as a recording material, contains whiteinorganic pigment particles on a backing material. In this connection,it is surely utilizable also to a plain paper.

A colored article according to the present invention is one obtained bycoloring a material to be colored with the above-described ink using anink-jet printer. A material to be colored is not limited in particularas long as it is the above-described recording material or othermaterials possible to be colored with an ink-jet printer.

To record on a recording material by an ink-jet recording methodaccording to the present invention, it is enough to record on arecording material in a usual method, for instance, after setting acontainer containing the above-described ink at a predetermined positionof an ink-jet printer. The ink-jet printer, for example, includes apiezo-type printer utilizing mechanical vibration, a bubble-jet printer(trade mark) utilizing foams generated by heating, and the like.

An ink according to the present invention does not precipitate, norseparate during storage. Furthermore, when an ink according to thepresent invention is used in ink-jet printing, a jetting device (an inkhead) is not clogged. An ink according to the present invention does notcause change in physical properties even under constant recirculationfor a comparatively long period by a continuous ink-jet printer, or onintermittent use by an on-demand style ink-jet printer.

An ink according to the present invention exhibits a clear cyan colorwhen a preferable colorant is used. Moreover, when an ink according tothe present invention is used, a recorded article especially excellentin ozone fastness, light fastness and water fastness can be obtained. Byusing it as a set of a deep-and-pale ink, a recorded article which isfurther excellent in ozone resistance, light fastness and water fastnesscan be obtained. Furthermore, by using it together with other inks suchas yellow, magenta and, if necessary, green, red, orange, blue, and thelike, color tones of a broad visible range can be exhibited, and arecorded article excellent in ozone fastness, light fastness and waterfastness can be obtained.

EXAMPLES AND COMPARATIVE EXAMPLES

Next, the present invention is more specifically explained by Examples.In this connection, “part” and “1%” in the specification are based onweight unless otherwise specified.

Example 1

Synthesis of the compound of Formula (1), wherein M is copper, which hastwo unsubstituted sulfamoyl groups and two substituted sulfamoyl groupsof Formula (3) positioned at the β-position, and in Formula (3), whereinY is a 2,5-disulfoanilino group, Z is an amino group, A is an ethylenegroup, and both of R17 and R18 are hydrogen atoms:

(1) Synthesis of Copper Phthalocyanine Tetrasulfonic Acid TetrasodiumSalt (a Substitution Type at the β-Position) (A Compound of FORMULA (6)Wherein, M is Cu, all of a, b, c and d are 1, and L is Na)

To a four-necked flask provided with a cooling tube, 40 parts ofsulfolane is added, and a temperature thereof was raised to 180° C. inone hour. Therein, 40 parts of a monosodium salt of 4-sulfophthalicacid, 4.5 parts of ammonium chloride, 55 parts of urea, 0.5 parts ofammonium molybdate, and 6 parts of copper (II) chloride were added,followed by stirring at the same temperature for 6 hours. After thereaction solution was cooled to 40° C., an objective material wasfiltered with Nutsche, and washed with 400 parts of methanol.Consequently, 300 parts of water was added to a wet cake obtained, andpH thereof was adjusted to 11 using a 48% aqueous solution of NaOH,followed by stirring at 80° C. for one hour. And while stirring, a 35%aqueous solution of hydrochloric acid was added thereto to make pH 3thereof, followed by gradual adding thereto 80 parts of sodium chloride.Deposited crystals were obtained by filtering and washed with 150 partsof a 20% aqueous solution of sodium chloride to obtain 90 parts of a wetcake. Then, 210 parts of methanol was added thereto, followed bystirring for one hour. Deposited crystals were separated by filtrationand washed with 300 parts of a 70% aqueous solution of methanol anddried to obtain 22.9 parts of copper phthalocyanine tetrasulfonic acidtetra sodium salt of a substitution type at the β-position, according toFormula (6), as blue crystals. λmax: 629 nm (in an aqueous solution).

(2) Synthesis of Copper Phthalocyanine Tetrasulfonic Acid Chloride (aSubstitution Type at the β-Position)

Into 79 parts of chlorosulfonic acid, 9.8 parts of a copperphthalocyanine tetrasulfonic acid tetrasodium salt were gradually addedwhile stirring at not higher than 60° C., and reaction was carried outat 120° C. for 4 hours. Then reaction solution was cooled to 80° C. andadded dropwise 47.6 parts of thionyl chloride over 30 min, and reactionwas carried out at 80° C. for 2 hours, then at 90° C. for one hour. Thereaction solution was cooled to not higher than 30° C. and slowly pouredinto 700 parts of ice water. Deposited crystals was separated byfiltration, and washed with 200 parts of a 2% aqueous solution ofhydrochloric acid cooled with ice to obtain 35.2 parts of a wet cake ofcopper phthalocyanine tetrasulfonic acid chloride.(3) Synthesis of the Compound of Formula (X-1) as shown below: (aCompound of Formula (X), wherein Y is a 2,5-Disulfoanilino Group, Z isan Amino Group, A is an Ethylene Group, both of R17 and R18 are HydrogenAtoms.)

Into 300 parts of ice water, 2.9 parts of Lipar OH and 96.5 parts ofcyanuric chloride were ed, followed by stirring for 30 min. Then, 150.8parts of a monosodium salt of aniline-2,5-disulfonic acid (purity:91.2%) were added thereto, and reaction was carried out at 10 to 15° C.for 2 hours, then at 25 to 35° C. for 2 hours, while retaining pHthereof at 2.7 to 3.0 by the addition of a 25% aqueous solution ofsodium hydroxide. Then, the reaction solution was cooled to not higherthan 10° C., and pH thereof was adjusted at 10.0 by the addition of a25% aqueous solution of sodium hydroxide and 60.7 parts of a 28% aqueousammonium to the reaction solution, and reaction was carried out at 10 to15° C. for 2 hours, then at 27 to 30° C. for 2 hours. Then, 600 parts ofethylenediamine was added therein, and reaction carried out at 80° C.for one hour. A solution amount thereof was adjusted to 2000 parts.Sodium chloride(200 parts) was added therein. Concentrated hydrochloricacid was consequently added drop-wise thereto to adjust pH at 1.0 and todeposit crystals. Thus deposited crystals were separated by filtrationand washed with 500 parts of a 20% aqueous solution of sodium chlorideto obtain 245.9 parts of a wet cake. The wet cake obtained (245.9 parts)was added into 1700 parts of methanol and suspended by adding thereto 90parts of water and stirring at 60° C. for one hour. Thereafter, byfiltration, washing with methanol and drying, 125.8 parts of a compoundof Formula (X-1) was obtained.

(4) Synthesis of an Objective Compound (a Compound Substituted at theβ-Position)

Into 200 parts of ice water, 35.2 parts of the wet cake of copperphthalocyanine tetrasulfonic acid chloride obtained in (2) was added andsuspended therein by stirring. After 10 min, a 28% aqueous ammonium wasadded dropwise therein while maintaining them at not higher than 5° C.,and pH thereof was adjusted to 9.0. Then, 2 parts of an aqueous ammoniumand an aqueous solution obtained by dissolving 8.5 parts of a compoundof Formula (X-1) into 100 parts of water, were poured into saidsuspension, and reaction was carried out at 10° C. for 2 hours, 20° C.for 2 hours, and then at 50° C. for one hour while adding a 28% aqueousammonium thereto to keep pH at 9.0. Water was added thereto to adjustthe solution amount to 500 parts, and 100 parts of sodium chloride wasadded therein to deposit crystals. Thus deposited crystals wereseparated by filtration and washed with 200 parts of a 20% aqueoussolution of sodium chloride to obtain 41.0 parts of a wet cake. Again,it was dissolved in water, and adjusted whole amount thereof to 400parts. The temperature thereof was raised to 60° C., and 80 parts ofsodium chloride were added thereto, then pH thereof was adjusted to 1.0by the addition of a 35% aqueous solution of hydrochloric acid todeposit crystals. Thus deposited crystals were separated by filtrationand washed with 200 parts of a 20% aqueous solution of sodium chlorideto obtain 51.5 parts of a wet cake. The wet cake obtained of 51.5 partswas added into 500 parts of methanol, and suspended therein by stirringat 60° C. for one hour. Thereafter, by filtering, washing with methanol,and drying, 8.9 parts of blue crystals were obtained. λmax of thiscompound was 608.5 nm (in an aqueous solution).

This compound has not less than 75% of a compound substituted at theβ-position, and, from the reaction and a added amount of a compound ofFormula (X-1), it seem to be a compound of Formula (9) (shown as a freeacid form without specifying substituted positions), wherein m is 2 andn is 2. However, as a result of analysis with a liquid chromatographmass analyzer, a sulfonic acid group was also confirmed. By consideringother analyzing results also, value of 1 (a sulfonic acid group) issupposed to be about 0.3, and value of n (a substituted sulfamoyl group)is supposed to be 0.5 to 2, and therefore the residue is m (anunsubstituted sulfamoyl group), and the total of l, m and n is 4 arethought to be close to an actual fact.

Example 2

Synthesis of the Phthalocyanine Colorant of Formula (1) which is thesame as Example 1 except that in the Colorant of the above DescribedExample 1, Substituents at the 1-Position were Changed to ThreeUnsubstituted Sulfamoyl Groups and One Substituted Sulfamoyl Group ofFormula (3)

Into 100 parts of ice water, 17.6 parts of the wet cake of copperphthalocyanine tetrasulfonic acid chloride obtained in Example 1 (2) wasadded and suspended therein by stirring. After 10 min, a 28% aqueousammonium was drop wise added while maintaining them at not higher than5° C., to adjust pH thereof to 9.0. Then, 0.5 parts of an aqueousammonium and an aqueous solution obtained by dissolving 2.1 parts of acompound of Formula (X-1) in 30 parts of water, were poured to theabove-described suspension. Reaction was carried out at 10° C. for 2hours, 20° C. for 2 hours, and then at 50° C. for one hour whilemaintaining pH at 9.0 by the addition of a 28% aqueous ammonium thereto.Water was added thereto to adjust the solution amount to 250 parts,followed by adding 50 parts of sodium chloride therein, to depositcrystals. Thus deposited crystals were separated by filtration andwashed with 100 parts of a 20% aqueous solution of sodium chloride toobtain 22.6 parts of a wet cake. Again, it was dissolved in water toadjust total amount thereof to 250 parts, temperature thereof was raisedto 60° C. and 12.5 parts of sodium chloride were added therto, and thenpH thereof was adjusted to 1.5 by the addition of a 35% aqueous solutionof hydrochloric acid to deposit crystals. Thus deposited crystals wereseparated by filtration, washed with 200 parts of a 20% aqueous solutionof sodium chloride to obtain 33.0 parts of a wet cake. The wet cakeobtained of 33.0 parts was added into 330 parts of methanol andsuspended therein by further adding 33 parts of water and stirring at60° C. for one hour. Thereafter, by filtering, washing with methanol anddrying, 4.1 parts of blue crystals were obtained. λmax of this compoundwas 602.5 nm (in an aqueous solution).

This compound has not less than 75% of a compound substituted at theβ-position, and from the reaction and a added amount of a compound ofFormula (X-1), it seem to be a compound of Formula (9) shown as a freeacid form without specifying substituted positions), wherein m is 3 andn is 1. However, as a result of analysis with a liquid chromatographmass analyzer, a sulfonic acid group was also confirmed. By consideringother analyzing results also, value of 1 (a sulfonic acid group) issupposed to be about 0.3, and value of n (a substituted sulfamoyl group)is supposed to be 0.3 to 1, and therefore the residue is m (anunsubstituted sulfamoyl group), and the total of l, m, and n is 4 arethought to be close to an actual fact.

Example 3

Synthesis of the Phthalocyanine Colorant of Formula (1) which is thesame as Example 1 except that, in the Colorant of the above DescribedExample 1, Substituents at the β-Position were Changed to oneUnsubstituted Sulfamoyl Group and Three Substituted Sulfamoyl Groups ofFormula (3).

Into 100 parts of ice water, 17.6 parts of the wet cake of copperphthalocyanine tetrasulfonic acid chloride obtained in Example 1 (2) wasadded and suspended therein by stirring. After 10 minutes, a 28% aqueousammonium was added dropwise while maintaining them at not higher than 5°C. to adjust pH thereof to 9.0. Then, 1.5 parts of an aqueous ammonium,and an aqueous solution obtained by dissolving 6.4 parts of a compoundof Formula (X-1) in 50 parts of water were poured to said suspension.Reaction was carried out at 10° C. for 2 hours, 20° C. for 2 hours, andthen at 50° C. for one hour while maintaining pH at 9.0 by the additionof a 28% aqueous ammonium thereto. Water was added thereto to adjust thesolution amount to 250 parts, followed by adding 50 parts of sodiumchloride therein to deposit crystals. Thus deposited crystals wereseparated by filtration and washed with 100 parts of a 20% aqueoussolution of sodium chloride to obtain 22.0 parts of a wet cake. Again,it was dissolved in water to adjust whole amount thereof to 250 parts,temperature thereof was raised to 60° C., and 50 parts of sodiumchloride was added thereto, and then pH thereof was adjusted to 1.0 bythe addition of 35% aqueous solution of hydrochloric acid to depositcrystals. Thus deposited crystals were separated by filtration andwashed with 100 parts of a 20% aqueous solution of sodium chloride toobtain 21.7 parts of a wet cake. The wet cake obtained of 21.7 parts wasadded into 220 parts of methanol and suspended therein by adding 10parts of water and stirring at 60° C. for one hour. Thereafter, byfiltering, washing with methanol and drying, 5.8 parts of blue crystalswere obtained. λmax of this compound was 612.0 nm (in an aqueoussolution).

This compound has not less than 75% of a compound substituted at theβ-position, and, from the reaction and added amount of a compound ofFormula (X-1), it seem to be a compound of Formula (9) (shown as a freeacid form without specifying substituted positions), wherein m is 1 andn is 3. However, as a result of analysis with a liquid chromatographmass analyzer, a sulfonic acid group was also confirmed. By consideringother analyzing results also, value of 1 (a sulfonic acid group) issupposed to be about 0.3, and value of n (a substituted sulfamoyl group)is supposed to be 0.8 to 3, and therefore the residue is m (anunsubstituted sulfamoyl group), and the total of l, m and n is 4 arethought to be close to an actual fact.

Example 4

Synthesis of the Phthalocyanine Colorant of Formula (1) which is thesame as Example 1 except that in the Colorant of the above DescribedExample 1, the Substituted Sulfamoyl Group of Formula (3) was Changed tothe Substituted Sulfamoyl Group derived from the Amine of Formula (X-2)as shown below:(1) Synthesis of the compound of Formula (X-2) as shown below: (acompound of Formula (X), wherein Y is a4,6,8-trisulfonaphthlene-2-yl-amino group, Z is an amino group, A is anethylene group; and both of R₁₇ and R₁₈ are hydrogen atoms.):

Into 100 parts of ice water, 0.6 parts of Lipar OH and 19.4 parts ofcyanuric chloride were added, followed by stirring for 30 min. Then,74.5 parts of a 2-aminonaphthlene-4,6,8-trisulfonic acid (purity: 51.4%)was added thereto, and reaction was carried out at 10 to 15° C. for 2hours, and then at 25 to 30° C. for 2 hours while maintaining pH thereofat 2.7 to 3.0 by the addition of a 25% aqueous solution of sodiumhydroxide. Then, said reaction solution was cooled to not higher than 5°C., and adjusted to pH 10.0 by the addition of a 25% aqueous solution ofsodium hydroxide. To this reaction solution, 12.1 parts of a 28% aqueousammonium solution was added, and reaction was carried out at 10 to 15°C. for 2 hours, and then at 27 to 30° C. for 2 hours. After the solutionamount thereof was adjusted to 700 parts, 140 parts of sodium chloride,and then a 35% hydrochloric acid were added to adjust pH at 6 and thusto deposit crystals. The crystals were separated by filtration to obtain149.3 parts of a wet cake. Then, 149.3 parts of the wet cake obtainedwas added into 120 parts of ethylenediamine and reaction was carried outat 80° C. for one hour. Into the reaction solution, 900 parts of2-propanol were added to carry out decantation. Methanol (1000 parts)was added to the residue obtained to deposit crystals. By filtering,washing with methanol and drying, 27.7 parts of white crystals wereobtained.

(2) The wet cake (17.6 parts) of copper phthalocyanine tetrasulfonicacid chloride obtained in Example 1 (2) were added into 100 parts of icewater to suspend therein by stirring. After 10 minutes, 28% aqueousammonium was added dropwise thereto while maintaining at not higher than5° C. to adjust pH thereof to 9.0. Next, 1.0 parts of an aqueousammonium solution, and an aqueous solution obtained by dissolving 5.8parts of a compound of Formula (X-1) in 50 parts of water, were pouredto said suspension and reaction was carried out at 10° C. for 2 hours,20° C. for 2 hours, and then at 50° C. for one hour while maintaining pHat 9.0 by the addition of a 28% aqueous ammonium thereto. Water wasadded thereto to adjust the solution amount to 200 parts and then 40parts of sodium chloride were added therein to deposit crystals. Thusdeposited crystals were separated by filtration and washed with 100parts of a 20% aqueous solution of sodium chloride to obtain 28.3 partsof a wet cake. Again, it was dissolved in water to adjust total amountthereof to 200 parts, temperature thereof was raised to 60° C., and then20 parts of sodium chloride were added thereto. Thereafter, pH thereofwas adjusted to 1.7 by the addition of a 35% aqueous solution ofhydrochloric acid to deposit crystals. Thus deposited crystals wereseparated by filtration, and then washed with 100 parts of a 10% aqueoussolution of sodium chloride to obtain 40.4 parts of a wet cake. The wetcake obtained of 40.4 parts was added into 320 parts of methanol, andsuspended therein by adding 16 parts of water and stirring at 60° C. forone hour. Thereafter, by filtering, washing with methanol and drying,4.5 parts of blue crystals were obtained. λmax of this compound was603.5 nm (in an aqueous solution).

This compound has not less than 75% of a compound substituted at theβ-position, and, from the reaction and added amount of a compound ofFormula (X-2), it seem to be a compound of Formula (12) (shown as a freeacid form without specifying substituted positions), wherein m is 2 andn is 2. However, as a result of analysis with a liquid chromatographmass analyzer, a sulfonic acid group was also confirmed. By consideringother analyzing results also, value of 1 is supposed to be about 0.3,and value of n is supposed to be 0.3 to 2, and therefore the residue ism, and the total of l, m and n is 4 are thought to be close to an actualfact.

Example 5

Synthesis of the Phthalocyanine Colorant of Formula (1) which is thesame as Example 1 except that in the Colorant of the above DescribedExample 1, the Substituted Sulfamoyl Group of Formula (3) was Changed tothe Substituted Sulfamoyl Group derived from the Amine of Formula (X-3)as shown below:(1) Synthesis of the compound of Formula (X-3) as shown below: (thecompound of Formula (X), wherein Y is a 2,5-disulfonanilino group, Z is2-sulfoethylamino group, A is an ethylene group, and both of R₁₇ and R₁₈are hydrogen atoms):

Into 160 parts of ice water, 0.1 parts of Lipar OH and 20 parts ofcyanuric chloride were added, followed by stirring for 30 min. Then,33.2 parts of a monosodium salt of aniline-2,5-disulfonic acid (purity:91.2%) was added thereoin, and reaction was carried out at 5 to 15° C.for 3 hours while maintaining pH thereof at 4.0 to 4.5 by the additionof a 10% aqueous solution of sodium carbonate. Then, to the reactionsolution, 13.8 parts of 2-aminoethanesulfonic acid was added, andreaction was carried out at 15° C. for 0.5 hour at pH of 6.5 to 7.0, andthen at 30° C. for 2 hours at pH of 8.0 to 8.5. To 400 parts of thereaction solution, 200 parts of 2-propanol and 60 parts of sodiumchloride were sequentially added to deposit crystals. The depositedcrystals were separated by filtration, washed with 2-propanol and driedat reduced pressure to obtain 130.2 parts of white crystals. Next, thusobtained 130.2 parts of the white crystals were added into 120 parts ofethylenediamine, and reaction was carried out at 80° C. for one hour.

Into said reaction solution, 800 parts of 2-propanol was added fordecantation. To the residue obtained, 600 parts of methanol was added todissolve the residue and the solution was filtrated. To the filtrate,1200 parts of 2-propanol was added to deposit crystals. The depositedcrystals were separated by filtration, washed with 2-propanol and driedto obtain 41.0 parts of white crystals.

(2) Into 100 parts of ice water, 17.6 parts of the wet cake of copperphthalocyanine tetrasulfonic acid chloride obtained in Example 1 (2)were added and suspended by stirring. After 10 minutes, 28% aqueousammonium water was added dropwise while maintaining them at not higherthan 5° C. to adjust pH thereof to 9.0. Thereafter, 1.0 parts of anaqueous ammonium solution, and an aqueous solution obtained bydissolving 5.1 parts of a compound of Formula (X-3) in 50 parts ofwater, were poured to said suspension and reaction was carried out at10° C. for 2 hours, 20° C. for 2 hours, and then at 50° C. for one hourwhile maintaining pH at 9.0 by the addition of a 28% aqueous ammoniumsolution thereto. Water was added thereto to adjust the solution amountto 200 parts and 40 parts of sodium chloride was added therein todeposit crystals. Thus deposited crystals were separated by filtrationand washed with 100 parts of a 20% aqueous solution of sodium chlorideto obtain 25.3 parts of a wet cake. Again, it was dissolved in water toadjust total amount thereof to 200 parts, temperature thereof was raisedto 60° C., 40 parts of sodium chloride were added thereto and pH thereofwas adjusted to 1.0 by the addition of a 35% aqueous solution ofhydrochloric acid to deposit crystals. Thus deposited crystals wereseparated by filtration, washed with 100 parts of a 20% aqueous solutionof sodium chloride to obtain 22.1 parts of a wet cake. The wet cakeobtained of 22.1 parts was added into 220 parts of methanol andsuspended therein by addition of 11 parts of water and stirring at 60°C. for one hour. Thereafter, by filtering, washing with methanol anddrying, 5.3 parts of blue crystals were obtained. λmax of this compoundwas 608.5 nm (in an aqueous solution).

This compound has not less than 75% of a compound substituted at theβ-position, and, from the reaction and added amount of a compound ofFormula (X-3), it seem to be a compound of Formula (13) shown as a freeacid form without specifying substituted positions), wherein m is 2 andn is 2. However, as a result of analysis with a liquid chromatographmass analyzer, a sulfonic acid group was also confirmed. By consideringother analyzing results also, value of 1 is supposed to be about 0.3,and value of n is supposed to be 0.5 to 2, and therefore the residue ism, and the total of l, m and n is 4 are thought to be close to an actualfact.

Example 6

Synthesis of the Phthalocyanine Colorant of Formula (1) which is thesame as Example 1 except that in the Colorant of the above DescribedExample 1, Substituents at the β-Position were Changed to 2.5Unsubstituted Sulfamoyl Groups and 1.5 Substituted Sulfamoyl Groups ofFormula (3).

The wet cake (17.6 parts) of copper phthalocyanine tetrasulfonic acidchloride obtained in Example 1 (2) was added into 100 parts of ice waterand suspended therein by stirring. After 10 minutes, 1.0 part of anaqueous ammonium solution, and an aqueous solution obtained bydissolving 3.2 parts of the compound of Formula (X-1) in 60 parts ofwater, were poured thereto and reaction was carried out at 17 to 20° C.for 9 hours while maintaining pH of 8 to 8.5 by the addition of a 28%aqueous ammonium thereto. Water was added thereto to adjust the solutionamount to 250 parts, and then 50 parts of sodium chloride therein wereadded to deposit crystals. Thus deposited crystals were separated byfiltration and washed with 100 parts of a 20% aqueous solution of sodiumchloride to obtain 33.0 parts of a wet cake. Again, it was dissolved inwater to adjust total amount thereof to 250 parts, after temperaturethereof was raised to 60° C., 12.5 parts of sodium chloride were addedthereto, and then pH thereof was adjusted to 1.5 by the addition of 35%aqueous solution of hydrochloric acid to deposit crystals. Thusdeposited crystals were separated by filtration and washed with 200parts of a 20% aqueous solution of sodium chloride to obtain 33.0 partsof a wet cake. The wet cake obtained of 33.0 parts was added into 330parts of methanol, and suspended therein by adding 33.0 parts of waterand stirring at 60° C. for one hour. Thereafter, by filtering, washingwith methanol and drying, 4.1 parts of blue crystals were obtained. λmaxof this compound was 612.1 nm (in an aqueous solution).

This compound has not less than 75% of a compound substituted at theβ-position, and, from the reaction and added amount of a compound ofFormula (X-1), it seem to be a compound of Formula (9) shown as a freeacid form without specifying substituted positions), wherein m is 3 andn is 1. However, as a result of analysis with a liquid chromatographmass analyzer, a sulfonic acid group was also confirmed. By consideringother analyzing results also, value of 1 (a sulfonic acid group) issupposed to be about 0.2, and value of n (a substituted sulfamoyl group)is supposed to be 0.8 to 1.5, and therefore the residue is m(unsubstituted sulfamoyl groups) (about 2.8 to 3), and the total of l, mand n is 4 are thought to be close to an actual fact.

Example 7 Evaluation of an Ink

(A) Preparation of an Ink

An ink was obtained by mixing and dissolving each component as describedin Table 8 below, and by filtrating with a 0.45 μm membrane filter(manufactured by Advantec Co., Ltd.). In this connection, ion-exchangedwater was used as water. Water and caustic soda (a pH adjustor) wereadded to make pH of the ink to 8 to 10, and make total amount thereof to100 parts. As for the ink, the ink using a compound of Example 1 wasnamed C-1, and inks using compounds of Examples 2 to 6 were named C-2 toC-6 in accordance with each number. TABLE 8 Each compound obtained inExamples 1 to 6 1.3 parts Water + Caustic soda 79.6 parts Glycerin 5.0parts Urea 5.0 parts N-methyl-2-pyrrolydone 4.0 parts IPA (Isopropylalcohol) 3.0 parts Butyl carbitol 2.0 parts Surfinol 104PG50 (Tradename: manufactured 0.1 parts by Nissin Chemical Co., Ltd.) Total 100.0parts

As a Comparative Example, a colorant for ink-jet recording generallyused as Direct Blue 199, product name: Projet Cyan 1 (manufactured byAbesia Chemical Co., Ltd.: Comparative Example 1) and a colorantsynthesized and purified by a method as described in Example 1 of theabove-described Reference 8 (Comparative Example 2) were formulated forink in the same method so that the same printing density was obtained onprinting as with inks of Examples 1 to 6 in Table 1. An ink using aproduct of Comparative Example 1 was referred to as C-A, and an inkusing a product of Comparative Example 2 was referred to as C-B.

(B) Ink-Jet Printing

Using an ink-jet printer (trade name BJ S630 manufactured by CanonInc.), ink-jet printing was conducted on two types of glossy Paper A (apaper for PM photograph, KA420PSK manufactured by Epson Co., Ltd) andglossy Paper B (Professional Photopaper, PR-101 manufactured by CanonInc.).

(C) Evaluation of a Recorded Image

1. Evaluation of Hue

Measurement of hue of a recorded print image was conducted bycolorimetry on a recording paper using a colorimetric system (GRETAGSPM50: manufactured by GRETAG Co., Ltd.), and a* and b* values weremeasured within the range of 50 to 90 of L* of a printed matter. Theresults were evaluated by 3 stages based on definition of preferable a*value being −50 to −10 and preferable b* value being −50 to −10.

∘: both a* and b* values reside in the preferable range.

Δ: only one of a* and b* values resides in the preferable range.

x: both a* and b* values reside outside of the preferable range.

2. Light Fastness Test

A test piece of a recorded print image was irradiated for 50 hours atlight intensity of 0.36 W/m², under conditions of temperature in avessel of 24° C. and humidity of 60% RH, using a xenon weatherometer(Type: Ci4000 manufactured by ATLAS Co., Ltd.). After the test, in therange of reflection density (D value) of 0.7 to 0.85, reflectiondensities before and after the test were measured using theabove-described calorimetric system. After the measurement, residualratio of colorants was calculated by (reflection density aftertesting/reflection density before testing)×100 (%), and were evaluatedby 3 stages;

∘: residual ratio of not lower than 70%;

Δ: residual ratio of 50 to 70%; and

x: residual ratio of lower than 50%.

3. Ozone Fastness

A test piece of a recorded print image was exposed for 3 hours at ozoneconcentration of 12 ppm, at temperature of 24° C. and at humidity of 60%RH in a vessel, using an ozone weatherometer (Type: OMS-H manufacturedby Suga Testing Machine Co., Ltd.). After the test, in the range ofreflection density (D value) of 0.7 to 0.85, reflection densities beforeand after the test were measured using the above-described calorimetricsystem. After the measurement, residual ratio of colorants wasdetermined by calculation based on (reflection density aftertesting/reflection density before testing)×100 (%), and evaluationresults were ranked by 3 stages:

∘: residual ratio of not lower than 70%;

Δ: residual ratio of 40 to 70%; and

x: residual ratio of lower than 40%.

4. Moisture Fastness

A test piece of a recorded print image was stored for 3 days attemperature of 50° C. and at humidity of 90% RH in a vessel, using athermo-hygrostat (manufactured by Ouyogiken-Sangyosya Co., Ltd.). Afterthe test, bleeding of a test piece was visually evaluated by 3 stages:

∘: bleeding is not confirmed;

Δ: slight bleeding is confirmed; and

x: much bleeding is confirmed.

Concerning recorded printing images with inks (C-1 to C-6) usingcompounds obtained in Examples 1 to 6, evaluation of hue and testresults of light fastness, ozone fastness and moisture fastness thereofare shown in Table 9 (Glossy paper A) and Table 10 (Glossy paper B).TABLE 9 Evaluation result of an ink: Glossy paper A Ink No. Hue LightFastness Ozone F. Moisture F. C-1 ∘ ∘ ∘ ∘ C-2 ∘ ∘ ∘ ∘ C-3 ∘ ∘ ∘ ∘ C-4 ∘∘ ∘ ∘ C-5 ∘ ∘ ∘ ∘ C-6 ∘ ∘ ∘ ∘ C-A ∘ ∘ x ∘ C-B ∘ ∘ x ∘

TABLE 10 Evaluation result of an ink: Glossy paper B Ink No. Hue LightFastness Ozone F. Moisture F. C-1 ∘ ∘ ∘ ∘ C-2 ∘ ∘ ∘ ∘ C-3 ∘ ∘ ∘ ∘ C-4 ∘∘ ∘ ∘ C-5 ∘ ∘ ∘ ∘ C-6 ∘ ∘ ∘ ∘ C-A ∘ ∘ x ∘ C-B ∘ ∘ x ∘

As apparent from Tables 9 and 10, a cyan ink using a compound of thepresent invention has excellent hue, along with excellent lightfastness, ozone fastness, and moisture fastness. It is apparent that ithas particularly excellent ozone fastness.

Example 8 An Ink Set

In an ink-jet printer (trade name: BJ F850 manufactured by Canon Inc.)having a cyan ink set provided with two concentrations of a pale cyanand a deep cyan, C-1 as a pale cyan ink and a genuine cyan inkmanufactured by Canon Inc. as a deep cyan ink, were mounted, and ink-jetprinting was conducted on two types of Glossy Paper A (a paper for PMphotograph, KA420PSK manufactured by Epson Co., Ltd) and Glossy Paper B(Professional Photopaper, PR-101 manufactured by Canon Inc.). As toprinting result, there was no generation of dot deletion, andsatisfactory clear prints even as full-colored image printing could beobtained. As the result, it was confirmed that an ink according to thepresent invention can be used in an ink-jet printer having a cyan inkset provided with two concentrations of a pale cyan and a deep cyan.

INDUSTRIAL APPLICABILITY

An ink using a compound of the present invention has a favorable hue asa cyan ink, and the like, and excellent light fastness, ozone fastnessand moisture fastness. Further, it does neither exhibit crystaldeposition, nor change in physical properties, nor change in color aftera long period of storage, and thus storage stability is favorable.Further, by combined use with other magenta ink and yellow ink, colortone can be obtained in a broad visible region. Therefore, the ink usinga phthalocyanine colorant according to the present invention, especiallya cyan ink, is extremely useful as an ink for ink-jet recording use.

1. A phthalocyanine colorant represented by Formula (1):

[in Formula (1), M represents a hydrogen atom, a metal atom, a metaloxide, a metal hydroxide, or a metal halide; R₂, R₃, R₆, R₇, R₁₀, R₁₁,R₁₄ and R₁₅ each independently represent an unsubstituted sulfamoylgroup represented by Formula (2), a substituted sulfamoyl grouprepresented by Formula (3), or a hydrogen atom, provided that at leastone of R₂, R₃. R₆, R₇, R₁₀, R₁₁, R₁₄ and R₁₅ is an unsubstitutedsulfamoyl group, and at least one thereof is a substituted sulfamoylgroup represented by Formula (3); and R₁, R₄, R₅, R₈, R₉, R₁₂, R₁₃ andR₁₆ represent hydrogen atoms; the sum of a number of an unsubstitutedsulfamoyl group and a number of a substituted sulfamoyl group is 2 to 4,and a number of an unsubstituted sulfamoyl group is 1 to 3 and a numberof a substituted sulfamoyl group is 1 to 3.]:

[in Formula (3), R₁₇ and R₁₈ each independently represent a hydrogenatom, a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted heterocyclic group, and asubstituted or unsubstituted alkenyl group; A represents a crosslinkinggroup, and adjacent R₁₇, R₁₈ and A may form a ring by bonding together;Y and Z each independently represent a halogen atom, a hydroxyl group, asulfonic acid group, a carboxyl group, an amino group, a substituted orunsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxygroup, a substituted or unsubstituted aryloxyl group, a substituted orunsubstituted heterocyclic oxy group, a substituted or unsubstitutedalkenyloxy group, a substituted or unsubstituted alkylamino group, asubstituted or unsubstituted cycloalkylamino group, a substituted orunsubstituted arylamino group, a substituted or unsubstitutedheterocyclic amino group, a substituted or unsubstituted alkenylaminogroup, a substituted or unsubstituted dialkylamino group, a substitutedor unsubstituted alkylthio group, a substituted or unsubstitutedarylthio group, a substituted or unsubstituted heterocyclic thio group,a substituted or unsubstituted alkenylthio group, provided that at leastone of Y and Z is a group having an ionic and hydrophilic group as asubstituent.]
 2. The phthalocyanine colorant according to claim 1,wherein Formula (1) according to claim 1 is represented by Formula (4)wherein M is Cu:

[wherein R₁ to R₁₆ mean the same as in Formula (1)].
 3. Thephthalocyanine colorant according to claim 1 or 2, wherein thecrosslinking group A is an alkylene, a cycloalkylene, or an arylenegroup.
 4. The phthalocyanine colorant according to any one of claims 1to 3, wherein in each of combinations of R₂ and R₃, R₆ and R₇, R₁₀ andR₁₁, and R₁₄ and R₁₅, one member of each combination is a hydrogen atom,and the other is an unsubstituted sulfamoyl group represented by Formula(2), a substituted sulfamoyl group represented by Formula (3) or ahydrogen atom, and among R₂, R₃, R₆, R₇, R₁₀, R₁₁, R₁₄ and R₁₅, at leastone is an unsubstituted sulfamoyl group and at least one is asubstituted sulfamoyl group represented by Formula (3).
 5. Thephthalocyanine colorant according to claim 1 or 2, wherein a substitutedsulfamoyl group of Formula (3) is a group represented by Formula (5) asshown below:

[in Formula (5), B represents an alkylene, arylene, or xylylene group; Dand E each independently represent a chlorine atom, a hydroxyl group, asulfonic acid group, a carboxyl group, an amino group, an alkoxy group(which may be substituted with a substituent selected from a groupconsisting of a sulfonic acid group, a carboxyl group, a hydroxyl group,a dialkylamino group, an arylamino group, an acetylamino group, analkoxy group, an aryl group, a cyano group and a halogen atom), aphenoxyl group (which may be substituted with one or two or moresubstituents selected from a group consisting of a sulfonic acid group,a carboxyl group, a ureide group, an alkyl group and an alkoxy group), anaphthoxyl group (which may be substituted with one or two or moresubstituents selected from a group consisting of a sulfonic acid groupand an acetylamino group), a benzyloxyl group (which may be substitutedwith a sulfonic acid group), a phenetyloxyl group (which may besubstituted with a sulfonic acid group), an alkylamino group (which maybe substituted with a substituent selected from a group consisting of asulfonic acid group, a carboxyl group, a hydroxyl group, an alkoxygroup, a dialkylamino group, an arylamino group, an aryl group, ahalogen atom and a cyano group), an anilino group (which may besubstituted with one or two or more substituents selected from a groupconsisting of a sulfonic acid group, a carboxyl group, a hydroxyl group,a dialkylamino group, an arylamino group, an acetylamino group, a ureidegroup, an alkyl group, an alkoxy group, a nitro group, a cyano group, aheterocyclic group and a halogen atom), a naphtylamino group (which maybe substituted with a sulfonic acid group or a hydroxyl group), abenzylamino group (which may be substituted with a sulfonic acid group),a phenetylamino group (which may be substituted with a sulfonic acidgroup), an alkylthio group (which may be substituted with a sulfonicacid group, a carboxylic group or a hydroxyl group) or an arylthio group(which may be substituted with one or two or more substituents selectedfrom a group consisting of a sulfonic acid group, a carboxyl group, ahydroxyl group, and an alkyl group), and at least one of D and E has, asa substituent, an ionic and hydrophilic group selected from a groupconsisting of a sulfonic acid group and a carboxyl group.]
 6. Thephthalocyanine colorant according to claim 1, wherein either one of Yand Z is an amino group, or a substituted or unsubstituted alkylaminogroup, and the other is a group other than a halogen and a hydroxylgroup.
 7. The phthalocyanine colorant according to claim 6, wherein agroup other than a halogen and a hydroxyl group is an arylamino groupsubstituted with a sulfonic acid group.
 8. The phthalocyanine colorantaccording to claim 1, wherein content of a colorant of Formula (1) is atleast 60% based on the total amount of colorants.
 9. The phthalocyaninecolorant according to any one of claims 1 to 8, wherein the colorant ofFormula (1) is obtained by subjecting the phthalocyanine colorant or thesalt thereof represented by Formula (6) to a reaction with achlorinating reagent to convert a sulfonic acid group to achlorosulfonic acid group, followed by further reaction with an organicamine represented by Formula (X) as shown below and an amidatingreagent:

[in Formula (6), M represents a hydrogen atom, a metal atom, a metaloxide, a metal hydroxide or a metal halide; L represents a hydrogenatom, an alkali metal ion, an alkali earth metal ion, an onium ion of anorganic amine or an ammonium ion; a, b, c and d is 0 or 1, and the sumthereof is an integer of 2 to 4.]:

[in Formula (X), R₁₇ and R₁₈ each independently represent a hydrogenatom, a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted heterocyclic group, and asubstituted or unsubstituted alkenyl group; A represents a crosslinkinggroup, and adjacent R₁₇, R₁₈ and A may form a ring by bonding together;Y and Z each independently represent a halogen atom, a hydroxyl group, asulfonic acid group, a carboxyl group, an amino group, a substituted orunsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxygroup, a substituted or unsubstituted aryloxyl group, a substituted orunsubstituted heterocyclic oxy group, a substituted or unsubstitutedalkenyloxy group, a substituted or unsubstituted alkylamino group, asubstituted or unsubstituted cycloalkylamino group, a substituted orunsubstituted arylamino group, a substituted or unsubstitutedheterocyclic amino group, a substituted or unsubstituted alkenylaminogroup, a substituted or unsubstituted dialkylamino group, a substitutedor unsubstituted alkylthio group, a substituted or unsubstitutedarylthio group, a substituted or unsubstituted heterocyclic thio group,a substituted or unsubstituted alkenylthio group, provided that at leastone of Y and Z is a group having an ionic and hydrophilic group as asubstituent.]
 10. A phthalocyanine colorant, which is obtained bysubjecting derivatives of 4-sulfophthalic acid to reaction withthemselves or subjecting a derivative of 4-sulfophthalic acid toreaction with a derivative of a phthalic acid (anhydride) in thepresence of a metallic compound to obtain a sulfometallo phthalocyaninecompound, which is reacted with a chlorinating reagent to convert asulfonic acid group to a chlorosulfonic acid group, followed by furtherreaction with an amidating reagent and an organic amine represented byFormula (X) as shown below:

[in Formula (X), R₁₇, R₁₈, A, Y and Z represent the same meaning asdescribed above.]
 11. The phthalocyanine colorant according to claim 10,wherein the crosslinking group A is an alkylene, a cycloalkylene, or anarylene group.
 12. The phthalocyanine colorant according to claim 10 or11, wherein the organic amine represented by Formula (X) is representedby Formula (X′) as shown below:

[in Formula (X′), B represents an alkylene, an arylene, or a xylylenegroup; D and E each independently represent a chlorine atom, a hydroxylgroup, a sulfonic acid group, a carboxyl group, an amino group, analkoxy group (which may be substituted with a substituent selected froma group consisting of a sulfonic acid group, a carboxyl group, ahydroxyl group, a dialkylamino group, an arylamino group, an acetylaminogroup, an alkoxy group, an aryl group, a cyano group and a halogenatom), a phenoxyl group (which may be substituted with one or two ormore substituents selected from a group consisting of a sulfonic acidgroup, a carboxyl group, a ureide group, an alkyl group and an alkoxygroup), a naphthoxyl group (which may be substituted with one or two ormore substituents selected from a group consisting of a sulfonic acidgroup and an acetylamino group), a benzyloxyl group (which may besubstituted with a sulfonic acid group), a phenetyloxyl group (which maybe substituted with a sulfonic acid group), an alkylamino group (whichmay be substituted with a substituent selected from a group consistingof a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkoxygroup, a dialkylamino group, an arylamino group, an aryl group, ahalogen atom and a cyano group), an anilino group (which may besubstituted with one or two or more substituents selected from a groupconsisting of a sulfonic acid group, a carboxyl group, a hydroxyl group,a dialkylamino group, an arylamino group, an acetylamino group, a ureidegroup, an alkyl group, an alkoxy group, a nitro group, a cyano group, aheterocyclic group and a halogen atom), a naphtylamino group (which maybe substituted with a sulfonic acid group or a hydroxyl group), abenzylamino group (which may be substituted with a sulfonic acid group),a phenetylamino group (which may be substituted with a sulfonic acidgroup), an alkylthio group (which may be substituted with a sulfonicacid group, a carboxylic group or a hydroxyl group), or an arylthiogroup (which may be substituted with one or two or more substituentsselected from a group consisting of a sulfonic acid group, a carboxylgroup, a hydroxyl group and an alkyl group); and at least one of D and Ehas, as a substituent, an ionic and hydrophilic group selected from agroup consisting of a sulfonic acid group and a carboxyl group.]
 13. Thephthalocyanine colorant according to any one of claims 10 to 12, whereinthe metallic compound is a copper compound.
 14. An ink characterized bycomprising, as a colorant component, the phthalocyanine colorantaccording to any one of claims 1 to
 13. 15. The ink according to claim14, which comprises an organic solvent.
 16. The ink according to claims14 or 15, which is for ink-jet recording use.
 17. An ink setcharacterized by using the ink according to any one of claims 14 to 16as at least one kind in an ink-jet printer which uses at least two kindsof cyan inks having different colorant concentrations.
 18. An ink-jetrecording method characterized by using, as an ink, the ink or the inkset according to any one of claims 14 to 17, in an ink- jet recordingmethod wherein recording is conducted onto a recording material byjetting ink droplets in response to recording signals.
 19. The ink-jetrecording method according to claim 18, wherein the recording materialis a sheet for information transmission.
 20. The ink-jet recordingmethod according to claim 19, wherein the sheet for informationtransmission is a surface-treated sheet and a sheet having an ink imagereceiving layer which contains white inorganic pigment particles on abacking material.
 21. A container comprising the ink or the ink setaccording to any one of claims 14 to
 17. 22. An ink-jet printercomprising the container according to claim
 21. 23. A colored productwhich is colored with the ink or the ink set according to any one ofclaims 14 to
 17. 24. A method for producing a phthalocyanine colorantcharacterized by being obtained by subjecting derivatives of4-sulfophthalic acid to reaction with themselves or subjecting aderivative of 4-sulfophthalic acid to reaction with a derivative of aphthalic acid (anhydride) in the presence of a copper compound to obtaina compound or a salt thereof, which is reacted with a chlorinatingreagent to convert a sulfonic acid group to a chlorosulfonyl group,followed by further reaction with an organic amine represented by theabove Formula (X) and an amidating reagent.
 25. A phthalocyaninecolorant which has not less than 60% of a compound substituted at theβ-position and not more than 40% of a compound substituted at theα-position in a phthalocyanine colorant represented by Formula (14) asshown below:

[wherein M represents a hydrogen atom, a metal atom, a metal oxide, ametal hydroxide or a metal halide; 1 includes 0 and lower than 1; m isnot smaller than 0.5 and not larger than 3; n is not smaller than 1 andnot larger than 3.5, and the sum of l, m and n is not smaller than 2 andnot larger than 4; R₁₇ and R₁₈ each independently represent a hydrogenatom, a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted heterocyclic group, and asubstituted or unsubstituted alkenyl group; and A represents acrosslinking group, and adjacent R₁₇, R₁₈ and A may form a ring bybonding together; Y and Z each independently represent a halogen atom, ahydroxyl group, a sulfonic acid group, a carboxyl group, an amino group,a substituted or unsubstituted alkoxy group, a substituted orunsubstituted cycloalkyloxy group, a substituted or unsubstitutedaryloxyl group, a substituted or unsubstituted heterocyclic oxy group, asubstituted or unsubstituted alkenyloxy group, a substituted orunsubstituted alkylamino group, a substituted or unsubstitutedcycloalkylamino group, a substituted or unsubstituted arylamino group, asubstituted or unsubstituted heterocyclic amino group, a substituted orunsubstituted alkenylamino group, a substituted or unsubstituteddialkylamino group, a substituted or unsubstituted alkylthio group, asubstituted or unsubstituted arylthio group, a substituted orunsubstituted heterocyclic thio group, a substituted or unsubstitutedalkenylthio group, provided that at least one of Y and Z is a grouphaving an ionic and hydrophilic group as a substituent.]
 26. Thephthalocyanine colorant according to claim 25, wherein either one of Yand Z is an amino group, or a substituted or unsubstituted alkylaminogroup, and the other is a group other than a halogen and a hydroxylgroup.
 27. The phthalocyanine colorant according to claim 25, wherein agroup other than a halogen and a hydroxyl group is an arylamino groupsubstituted with a sulfonic acid group.
 28. The phthalocyanine colorantaccording to claim 25, wherein M represents a copper atom; A representsa divalent crosslinking group having carbon atoms of 1 to 6; 1 includes0 and smaller than 1; m is not smaller than 0.5 and not larger than 3; nis not smaller than 1 and not higher than 3; and the sum of l, m and nis 2 to 4; both R₁₇ and R₁₈ represent hydrogen atoms; Y and Z eachindependently represent an amino group, a substituted or unsubstitutedalkylamino group, a substituted or unsubstituted arylamino group, asubstituted or unsubstituted dialkylamino group, provided that at leastone of Y and Z is a group having an ionic and hydrophilic group as asubstituent.